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MORISAWA Yusuke

    Department of Science　Associate Professor
Last Updated :2024/04/25

Researcher Information

URL

Research funding number

  • 60510021

ORCID ID

Researcher ID

  • F-5095-2010

J-Global ID

Profile

  • Research Topics:
    ・Study of the electronic state of molecules in the condensed phase using attenuated total reflectance spectroscopy in the far and deep ultraviolet regions
    ・Development of a new analytical method using far ultraviolet, near infrared and THz spectroscopy
    ・Research on near-infrared spectral absorption intensity due to intermolecular interactions such as hydrogen bonds

Research Interests

  • Analytical Chemistry with Spectroscopy   Near Infrared Spectroscopy   Molecular Spectroscopy   電子状態   水素結合   減衰全反射遠紫外分光法   高分子   表面分析   テラヘルツ分光   

Research Areas

  • Nanotechnology/Materials / Basic physical chemistry
  • Nanotechnology/Materials / Analytical chemistry
  • Nanotechnology/Materials / Crystal engineering
  • Nanotechnology/Materials / Applied materials

Academic & Professional Experience

  • 2016/12 - Today  Kindai UniversityResearch Institute of Bio-coke准教授
  • 2016/04 - Today  Kindai UniversitySchool of Science and engineeringAssociate Professor
  • 2012/04 - 2016/03  Kinki UniversitySchool of Science and engineeringLecturer
  • 2008/04 - 2012/03  Kwansei Gakuin UniversitySchool of Science and TechnologyPostdoctoral fellow
  • 2005/10 - 2008/03  台湾中央研究院 原子分子研究所博士後研究員

Education

  • 2000/04 - 2005/03  Kyoto University  Graduate School of Science  Department of Chemistry
  • 1998/04 - 2000/03  Kyoto University  Graduate School of Science  Department of Chemsitry
  • 1994/04 - 1998/03  Kwansei Gakuin University  School of Science  Department of Chemistry

Association Memberships

  • Japanese Council for Near Infrared Spectroscopy   Society for Applied Spectroscopy   THE SPECTROSCOPICAL SOCIETY OF JAPAN   THE JAPAN SOCIETY FOR ANALYTICAL CHEMISTRY   THE CHEMICAL SOCIETY OF JAPAN   

Published Papers

  • Yukihiro Ozaki; Yusuke Morisawa; Ichiro Tanabe
    Chemical Society Reviews Royal Society of Chemistry (RSC) 53 (4) 1730 - 1768 0306-0012 2024/01 [Refereed]
     
    This review reports the recent progress on ATR-far ultraviolet (FUV) spectroscopy in the condensed phase.
  • Akifumi Ikehata; Yusuke Morisawa
    The Journal of Physical Chemistry B American Chemical Society (ACS) 127 (28) 6325 - 6332 1520-6106 2023/07 [Refereed][Invited]
     
    Although determining the chemical states of salts and ions is critical in numerous fields, such as elucidating biological functions and maintaining food quality, the current direct observation methods are insufficient. We propose a spectral analysis method of directly observing the phase transitions of NaCl solutions using the changes in the charge-transfer-to-solvent band and the absorption band representing the first electron transition (Ã ← X̃) of H2O. The intensities of these bands may be observed using attenuated total reflection far-ultraviolet spectroscopy. According to the well-known phase diagram of aqueous NaCl, we observe spectral changes during freezing–thawing and may spectroscopically detect the phase transitions from liquid to mixed liquid–solid and solid phases, including eutectic crystals, in addition to their coexistence curves.
  • Supitchaya Cherdkeattikul; Yusuke Morisawa; Nami Tagami-Kanada; Tamio Ida
    Fuel Elsevier BV 342 127835 - 127835 0016-2361 2023/06 [Refereed]
     
    This research focuses on the chemical transformation of a solid biofuel, biocoke, produced under subcritical water. The authors aim to study via attenuated total reflectance infrared spectroscopy (ATR-FTIR) the effect of additional lignocellulose (cellulose, hemicellulose, and lignin) substances on the structural reaction and the biocoke compressive strength for industrial quality control purposes. Principal component regression is used to analyze the structural alterations between mixtures, materials, and biocoke samples and then determine the correlation between these changes and the biocoke’s maximum compressive strength. The results show a relationship between changes in the 1800–1500 and 800–400 cm−1 regions of FTIR and the maximum compressive strength of the biocoke. Lignin cleavage caused changes in the 1800–1500 cm−1 region. The greater the lignin concentration, the more clearly a reaction was detected. Alteration in the 800–400 cm−1 region resulted from higher cellulose content in the biocoke, which decreased the biocoke’s maximum compressive strength. The hemicellulose content did not show any correlation with the structural changes in this study setup.
  • Harumi Sato; Yusuke Morisawa; Satoshi Takaya; Yukihiro Ozaki
    Applied Spectroscopy SAGE Publications 76 (7) 000370282210869 - 000370282210869 0003-7028 2022/04 [Refereed]
     
    Inter- and intramolecular hydrogen bonding and their temperature-dependent changes in a poly(4-vinylphenol)/poly(methyl methacrylate)(PVPh 30%/PMMA 70%) blend were investigated using near-infrared (NIR) and infrared (IR) spectroscopy. Band assignments of the fundamentals and first overtones of the OH stretching mode of a free OH group and OH groups in C=O···HO and OH···OH (dimer, trimer, and oligomer) hydrogen bonding of PVPh 30%/PMMA 70% were carried out by comparison between its NIR and IR spectra and comparison with NIR and IR spectra of phenol. The comparison of the NIR spectra of the PVPh 30%/PMMA 70% blend (hereafter, we denote it as PVPh30%) with the corresponding IR spectra reveals that to observe bands arising from the free OH and OH···OH dimer, which is a weaker hydrogen bonding, NIR is better while to investigate bands originating from OH groups in the OH···O=C and OH···OH (oligomer) hydrogen bonds, which are stronger hydrogen bonding, IR is better. Thus, a combination of IR and NIR spectroscopy has provided convincing results for the hydrogen bonding of PVPh30%. The relative intensity of the two bands at 7058 and 6921 cm–1 (I7058/I6921) due to the first overtones of the OH stretching modes of the free OH group and the OH group in the dimer, respectively, increases significantly above 90 °C, which is close to Tg of PVPh. In concomitance with the intensity increase in the relative intensity of the free OH band, the intensity of a band at 1706 cm–1 due to the C=O stretching mode of the C=O···HO hydrogen bond of PVPh30% decreases above 90°C. These results suggest that above the Tg of PVPh the C=O···HO hydrogen bond is broken gradually and that the free OH increases. Of note is that below Tg the intensities of NIR bands due to the OH first overtones of free OH group and OH groups in the OH···OH dimer gain intensity in parallel with temperature increase, and above Tg the intensity of the band derived from the OH···OH group increases linearly much slower than that of the band due to the free OH. Moreover, a band due to an OH···OH oligomer decreases linearly. Hence, it is very likely that the OH···OH oligomers dissociate into free OH groups. Anharmonicity of O–H bonds, which is sensitive to a hydrogen bond, was estimated for the free OH and OH bonds in the C=O···HO and OH···OH (dimer, trimer, and oligomer) hydrogen bonding by comparison between the NIR and IR spectra in the OH stretching band regions.
  • Kosuke Hashimoto; Yusuke Morisawa; Mariagrazia Tortora; Barbara Rossi; Yukihiro Ozaki; Hidetoshi Sato
    Applied Spectroscopy SAGE Publications 76 (7) 793 - 800 0003-7028 2022/04 [Refereed]
     
    Attenuated total reflection-far-ultraviolet (ATR-FUV) spectra in the 145 – 250 nm region were studied for four kinds of proteins (two α-helix rich proteins; bovine serum albumin (BSA) and lysozyme, and two β-sheet rich proteins; concanavalin A and γ-globulin) in different solutions (pure water and phosphate buffered saline (PBS)) with different concentrations. All the spectra show a band at 191 nm due to the π－π* transition of amide bonds of the proteins. The wavelength of the band does not change with their second structures, suggesting that the corresponding electronic transition mode is localized and polarized in the direction that is not affected by the difference in the peptide folding. The intensity of the 191 nm band differs with the concentration of salt in the solution, suggesting that the band intensity reflects the adsorption density of a protein on the internal reflection element (IRE) made of a sapphire glass prism. According to the intensity changes of the band at 191 nm, it is revealed that the properties in adsorption are different from one protein to another. It is assumed that there are two types of forces on the protein adsorption; one is that among the molecules, and the other is that between a molecule and a substrate. The origin of force includes localized electrostatic polarity and affinity to water. The ions in the solvent give a marked effect on these forces, resulting in the difference in the response to adsorption density against the salt concentration in the solvent.
  • Nami Ueno; Masato Takegoshi; Anna Zaitseva; Yukihiro Ozaki; Yusuke Morisawa
    The Journal of Chemical Physics AIP Publishing 156 (7) 074705-1 - 074705-9 0021-9606 2022/01 [Refereed][Invited]
     
    ABSTRACT The demand for Li secondary batteries is increasing, with the need for batteries with a higher level of performance and improved safety features. The use of a highly concentrated aqueous electrolyte solution is an effective way to increase the safety of batteries because it is possible to use “water-in-salt” (WIS) and “hydrate-melt” (HM) electrolytes for practical applications. These electrolytes exhibit a potential window of >3.0 V, which is attributed to the difference between the HOMO and the LUMO energies of the n orbital of the pure water molecules and that of the water molecules in the hydration shells of a metal ion, according to theoretical predictions. Thus, in the present study, the attenuated total reflectance (ATR)-far-ultraviolet (FUV) spectra of water and super-concentrated aqueous solutions, such as WIS and HM using a Li salt, were experimentally investigated. The effects of anions, cations, and deuteriums on the ATR-FUV spectra were examined. The ATR-FUV method is an excellent means of studying highly concentrated aqueous salt solutions. The results suggest that the transition energy of water molecules in an ultrahighly concentrated aqueous electrolyte containing HM and WIS increased by nearly 0.4 eV (corresponding to an energy shift of over 10 nm) compared to an aqueous electrolyte with a typical water concentration. It was also revealed that the transition energy of water changes depending on the environment of the non-bonding electron, which is directly connected with or affected by hydrogen bonding with other water molecules or directly connected with Li+
  • Swapnil Singh; Mateusz Majer; Mirosław Antoni Czarnecki; Yusuke Morisawa; Yukihiro Ozaki
    Applied Spectroscopy SAGE Publications 76 (1) 28 - 37 1943-3530 2022/01 [Refereed]
     
    This work provides new insight into assembling of phenol in various solvents and competition between different kinds of interactions. To examine both weak and strong interactions, we selected a series of non-aromatic and aromatic solvents. Infrared spectra were measured at low (0.05 M) and high (2 M) phenol content. In addition, we performed density functional theory calculations of the structures and harmonic vibrational spectra of 1:1 complexes of phenol with the solvents and the associates of phenol from dimer to tetramer. Based on these results, we divided the solvents into three groups. The first group consists of non-aromatic solvents weakly interacting with phenol. Depending on the concentration, molecules of phenol in these solvents remain non-bonded or self-associated. In diluted solutions of phenol in chlorinated non-aromatic solvents do not appear free OH groups, since they are involved in a weak OH···Cl interaction. It is of note that in diluted solutions of phenol in tetramethyl ethylene both the non-bonded and bonded OH coexists due to solvent–solvent interactions. The second group consists of aromatic solvents with methyl or chlorine substituents. At low concentration, the molecules of phenol are involved in the phenol–solvent OH···π interaction and the strength of these interactions depends on the solvent properties. At a higher phenol content an equilibrium exists between phenol–solvent OH···π and phenol–phenol OH···OH interactions. Finally, the third group includes the aromatic and non-aromatic solvents with highly polar group (C≡N). In these solvents, regardless of the concentration all molecules of phenol are involved in the solute–solvent OH···NC interaction. Comparison of the experimental and theoretical band parameters reveals that molecules of phenol in non-aromatic solvents prefer the cyclic associates, while in the aromatic solvents they tend to form the linear associates.
  • Yukihiro Ozaki; Krzysztof B. Beć; Yusuke Morisawa; Shigeki Yamamoto; Ichiro Tanabe; Christian W. Huck; Thomas S. Hofer
    Chemical Society Reviews Royal Society of Chemistry (RSC) 50 (19) 10917 - 10954 0306-0012 2021/10 [Refereed]
     

    The purpose of this review is to demonstrate advances, challenges and perspectives of quantum chemical approaches in molecular spectroscopy of the condensed phase.

  • Yusuke Morisawa; Yugo Higaki; Yukihiro Ozaki
    The Journal of Physical Chemistry A American Chemical Society (ACS) 125 (37) 8205 - 8214 1089-5639 2021/09 [Refereed]
     
    Far-ultraviolet (FUV) spectra were measured for cyclohexane, methyl cyclohexane, six isomers of dimethyl cyclohexane, and cis- and trans-decalin. Attenuated total reflection-FUV (ATR-FUV) spectroscopy, which we originally proposed, provides systematic information about the excitation states of saturated organic molecules and the hyperconjugation of σ bonds. The FUV spectra of cyclohexane and methyl cyclohexane in neat liquids showed a band with central wavelengths near 155 and 162 nm. The simulation spectrum of cyclohexane calculated by time-dependent density-functional theory (TD-DFT) (CAM-B3LYP/aug-cc-pVTZ) gives two bands at 146 and 152 nm owing to the transition from HOMO-2 to Rydberg 3pz (Tb) and those from HOMO and HOMO-1 to Rydberg 3px/3py (Ta), respectively. The simulation spectrum of methyl cyclohexane with the equatorial substituent has peaks at approximately the same positions as cyclohexane. The calculated molar absorption coefficient is larger than that of cyclohexane, estimating the observed FUV spectra very well. The FUV spectra of dimethyl cyclohexane with two methyl substituents at the equatorial positions (trans-1,2-, cis-1,3-, and trans-1,4-) and trans-decalin had similar features to those of cyclohexane and methylcyclohexane. The TD-DFT calculations revealed that the shoulders at the shorter- and longer-wavelength sides of the band center of dimethyl cyclohexane (with methyl substituents at equatorial positions) and trans-decalin are assigned to Tb and Ta, respectively. In the case of dimethyl cyclohexane with one methyl substituent in the axial position (cis-1,2-, trans-1,3-, and cis-1,4-) and cis-decalin, the band caused by Tb decreased compared to those of the other compounds. The decrease in intensity and the longer-wavelength shift of the Tb band for dimethyl cyclohexane (with one methyl group at the axial position) and cis-decalin revealed that the band on the longer-wavelength side was assigned to the overlap band of Ta and Tb. The reason for such a large spectral alternation for the axial substitution may be the increase in the orbital energy of HOMO-2, which has its electron density concentrated at the axial C–H bond. Regarding the effect of the hyperconjugation of C–C and C–H σ orbitals, the second perturbation energies of the interaction between Cα–Hax and Cβ–Hax were estimated for molecules by natural bond orbital (NBO) analysis. There is a correlation between the orbital energies of HOMO-2 and the changes in vicinal interaction by axial substitution.
  • Czarnecki, M.A.; Morisawa, Y.; Katsumoto, Y.; Takaya, T.; Singh, S.; Sato, H.; Ozaki, Y.
    Physical Chemistry Chemical Physics Royal Society of Chemistry ({RSC}) 23 (35) 19188 - 19194 1463-9076 2021/08 [Refereed]
     
    Near-infrared spectroscopy (NIR) and DFT calculations were applied to study solvent effect on competition between weak and strong interactions in phenol solutions.
  • Morisawa, Y.; Tanimura, E.; Ehara, M.; Sato, H.
    Applied Spectroscopy SAGE Publications 75 (8) 971 - 979 1943-3530 2021/05 [Refereed][Invited]
     
    In this study, we explored the electronic structure of the surfaces of polyethylene samples having different crystallinities using attenuated total reflection (ATR) far-ultraviolet (FUV) spectroscopy and quantum chemical calculations. Specifically, the ATR-FUV spectra of five types of high-density polyethylene (HDPE), six types of linear low-density PE (LLDPE), and seven types of low-density PE (LDPE) were obtained. All the spectra contained an intense band near 156 nm and a broad band between 180 and 190 nm. Transmission spectra were obtained for the thin-film (30 µm) PE samples between 165 and 250 nm. In this region, the HDPE films show very low-intensity bands. In contrast, the transmission spectra of the LLDPE and LDPE samples yielded weak-to-medium and medium-intensity bands around 180–190 nm, respectively. In addition, to understand the differences in the absorption spectra among the PEs observed, we simulated the spectra of n-pentane as a PE crystal model using time-dependent density functional theory and found that the common intense band at 156 nm is due to the σ (C(2p)–H)→Rydberg 3s, 3p transition. The absorption bands near 180–190 nm may correspond to aggregates of numerous molecular chains in the amorphous parts of the LLDPE and LDPE samples.
  • Yukihiro Ozaki; Yusuke Morisawa; Ichiro Tanabe; Krzysztof B Beć
    Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy 253 119549 - 119549 2021/02 [Refereed][Invited]
     
    Far-ultraviolet (FUV) spectroscopy in the region of 140-200 nm of condensed-phase has received keen interest as a new electronic spectroscopy. The introduction of the attenuated total reflection (ATR) technique to the FUV region has opened a new avenue for FUV spectroscopy of liquids and solids. ATR-FUV spectroscopy enables the study of electronic structures and transitions of most types of molecules. It also holds great promise for a variety of applications, i.e., from the application to basic sciences to practical applications. In this review, the characteristics and advantages of ATR-FUV spectroscopy in the condensed phase are described first; then, a brief historical overview is provided. Next, the ATR-FUV spectroscopy instrumentation is outlined. After these introductory parts, a variety of AFT-FUV spectroscopy applications are introduced, starting from applications to investigations of electronic structure and transitions of alkanes, graphenes, and polymers. Then, time-resolved ATR-FUV spectroscopy is discussed. The applications to materials research, such as the research on inorganic semiconductors and ionic liquids, follow. In the last part, the FUV spectroscopy perspective is emphasized.
  • Yukihiro Ozaki; Shigeaki Morita; Yusuke Morisawa
    Near-Infrared Spectroscopy Springer Singapore 63 - 82 2021
  • Yukihiro Ozaki; Yusuke Morisawa
    Near-Infrared Spectroscopy Springer Singapore 11 - 35 2021
  • Urszula Szczepaniak; Kazunori Ozaki; Kaito Tanaka; Yuma Ohnishi; Yoriko Wada; Jean Claude Guillemin; Claudine Crépin; Robert Kołos; Yusuke Morisawa; Hal Suzuki; Tomonari Wakabayashi
    Journal of Molecular Structure 1214 0022-2860 2020/08 [Refereed]
     
    © 2020 Elsevier B.V. Cyanopolyyne molecules, HC9N and HC11N, were isolated in solutions and UV, IR, and resonance Raman spectra were measured for the study of their electronic and vibrational properties. Strong signals were observed both in the IR and resonance Raman spectra for the stretching vibrational mode of the sp-hybridized linear carbon chain in the electronic ground state, i.e., σ4 at 2141 cm−1 for HC9N and σ6 at 2105 cm−1 for HC11N. Trapped in cryogenic solid acetonitrile matrix hosts at 20 K, transitions in phosphorescence, a˜3Σ+ → X˜1Σ+, were observed for HC9N at 582.3 nm (0–0) and longer wavelengths and for HC11N at 643.7 nm (0–0) and longer wavelengths. Electronic transitions in the UV, 1Σ+ ← X˜1Σ+, were elucidated by phosphorescence excitation mapping to observe asymmetric patterns with sharp emission-absorption features explainable by Shpolsky effects. For HC9N, three distinct trapping sites were discernible in solid acetonitrile, while the phosphorescence spectra were blurred in solid n-hexane. The observed phosphorescence lifetime of HC9N was longer than that of HC11N, comparable to the trend reported for the series of cyanopolyyne molecules in solid krypton matrix hosts.
  • Manuel J. Schuler; Thomas S. Hofer; Yusuke Morisawa; Yoshisuke Futami; Christian W. Huck; Yukihiro Ozaki
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS ROYAL SOC CHEMISTRY 22 (23) 13017 - 13029 1463-9076 2020/06 [Refereed]
     
    Previous measurements of fundamental, first-, second- and third overtones of the OH-stretching vibration of phenol and 2,6-difluoro-phenol by use of visible (Vis), near-infrared (NIR) and infrared (IR) spectroscopy revealed an oscillating pattern in the intensity quotient between the two kinds of solvents, carbon tetrachloride andn-hexane, upon increase of the vibrational quantum number, which could not be reproduced utilizing quantum mechanical calculations in implicit solvation. In the present study this phenomenon was successfully explained for the first time, employing an explicit consideration of solute-solvent interactions in combination with modern grid-based methods to solve the time-independent Schrodinger equation. The capabilities of this framework of (i) not requiring any assumptions on the form of the resulting wave function, (ii) focusing the description on the vibrational mode of interest and (iii) taking solute-solvent interactions explicitly into account are a particularly lucid example of the advantages in applying state-of-the-art approaches in investigations of challenging vibrational quantum problems. The property of grid-based methods being directly applied onto any given potential energy grid together with point (i) enable to analyse the impact of mechanical- and electrical anharmonicity independently. Especially the detailed investigation of the latter contribution when moving from a harmonic to an anharmonic potential in conjunction with the explicit consideration of solvent effects at the example of an actual chemical system (i.e.not discussing these effects employing mere model potentials) demonstrate the manifold benefit achieved using the applied DFT/Numerov strategy.
  • Supitchaya Cherdkeattikul; Yusuke Morisawa; Tamio Ida
    ANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEMISTRY 36 (6) 723 - 729 0910-6340 2020/06 [Refereed]
     
    This present research applied the ATR-FTIR technique and principle component analysis (PCA) to investigate molecular surface changes in pre-carbonized solid biomass, called Kindai Bio-coke (BIC) and Japanese cedar. The product is utilized as an alternative to coal coke in the cupola furnace in the steel industry in order to reduce CO2 emissions. The aim is to explore key elements for improving the BIC product applications from the fundamental molecular scale by using PCA to distinguish between changes during the BIC transformation and the differences in BIC samples. Results revealed that transformation occurred at the surface of Japanese cedar raw materials and Japanese cedar BIC. Major changes were observed in the O-H, C-H and C-O stretching regions. The intensity of the IR bands attributed to aliphatic methyl (CH3) and methylene (CH2) stretching modes increased, while a weak O-H stretching intensity associated with BIC hydrophobic characteristic decreased.
  • Ueno Nami; Morisawa Yusuke
    The Proceedings of the Symposium on Environmental Engineering The Japan Society of Mechanical Engineers 2020.30 205  2020 
    FT-NIR spectroscopy has the potential to be an index for the degree of the formation of BICs using the changes in the hydrogen bonding or CH stretching vibration in terminal groups between the materials (reagents such as cellulose and cellobiose, botanical wastes from coffee beans and tealeaves) and various processing conditions of BICs. FT-NIR spectroscopy is a grate method for the BICs analysis because it is able to measure the vibrational spectra without destruction and pre-preparation for the spectroscopic measurement. The other reason why NIR is that this spectroscopy is hard to include noises from some contained materials in BICs. In the other hand, NIR spectra need the statistics analysis called “chemometrics” because these spectra show very broad and overlapped band. Changes of these overlapped bands are easier to interpret than MIR regions because MIR region has larger amount of information from many kinds of vibrations. Results of the chemometrics need the careful consideration for the changes between analytical results and intentionally perturbations because sometimes chemometrics results do not have the chemical meaning. Raman and THz spectroscopy are used to understand the actual chemical changes with perturbations by comparing with the results of statistical analysis.
  • Nami Ueno; Tomonari Wakabayashi; Yusuke Morisawa
    ANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEMISTRY 36 (1) 91 - 93 0910-6340 2020/01 [Refereed]
     
    Attenuated total reflectance-far ultraviolet (ATR-FUV) spectra of Li+ and polyether ligands, such as glymes and poly (ethylene glycol) (PEG), in solution give information about changes in the electronic states of the ligands. From the ATR-FUV spectra, the coordination numbers between Li+ and monoglyme, diglyme, triglyme, and PEG400 were determined to be 4, 5, 6, and 5, respectively. Our results indicate that Li+ is coordinated only by the ligands rather than its counter-ions.
  • Nami Ueno; Tomonari Wakabayashi; Harumi Sato; Yusuke Morisawa
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 123 (50) 10746 - 10756 1089-5639 2019/12 [Refereed]
     
    This study investigates the electronic transitions of complexes of lithium with polyethylene glycol (PEG) by the absorption bands of solvent molecules via attenuated total reflectance spectroscopy in the far-UV region (ATR-FUV). Alkali-metal complexes are interesting materials because of their functional characteristics such as good ionic conductivity. These complexes are used as polymer electrolytes for Li batteries and as one of the new types of room-temperature ionic liquids, termed solvation ionic liquids. Considering these applications, alkali-metal complexes have been studied mainly for their electrochemical characteristics; there is no fundamental study providing a clear understanding of electronic states in terms of electronic structures for the ground and excitation states near the highest occupied molecular orbital-lowest occupied molecular orbital transitions. This study explores the electronic transitions of ligand molecules in alkali-metal complexes. In the ATR-FUV spectra of the Li-PEG complex, a decrease in intensity and a large blue shift (over 4 nm) were observed to result from an increase in the concentration of Li salts. This observation suggests the formation of a complex, with coordinate bonding between Li+ and the O atoms in PEG. Comparison of the experimental spectrum with a simulated spectrum of the Li-PEG complex calculated by time-dependent density functional theory indicated that changes in the intensities and peak positions of bands at approximately 155 and 177 nm (pure PEG shows bands at 155, 163, and 177 nm) are due to the formation of coordinate bonding between Li+ and the O atoms in the ether molecule. The intensity of the 177 nm band depends on the number of residual free O atoms in the ether, and the peak wavelength at approximately 177 nm changes with the expansion of the electron clouds of PEG. We assign a band in the 145-155 nm region to the alkali-metal complex because we observed a new band at approximately 150 nm in the ATR-FUV spectra of very highly concentrated binary mixtures.
  • Asuka Endo; Miho Hatanaka; Nami Ueno; Yusuke Morisawa; Tomonari Wakabayashi
    LOW TEMPERATURE PHYSICS AMER INST PHYSICS 45 (7) 689 - 696 1063-777X 2019/07 [Refereed]
     
    The A-X transition of diatomic bismuth, Bi-2, was revisited by laser induced fluorescence in solid Ne at 3K. Molecular constants, i.e., vibrational frequencies of 137cm(-1) and 174cm(-1), were reproduced for the upper and lower electronic states as reported by Bondybey et al. [Chem. Phys. Lett. 76, 30 (1980)]. Two-dimensional mapping of emission spectra confirmed satellite bands in higher and lower excitation/emission energies for each of the major bands in the vibrational progression of v '-v '' (v '=0-5, v ''=5-12). Based on the molecular orbital calculations, presence of clusters, Bi2Nen (n=1-6), is proposed for possible carriers of the observed satellites. For the relatively large matrix shift of similar to 67cm(-1) in solid Ne for the term energy of the A state, the diatomic bismuth is supposed to exist as a linearly coordinated cluster of Bi2Ne in the matrix.
  • Sata, R.; Suzuki, H.; Ueno, N.; Morisawa, Y.; Hatanaka, M.; Wakabayashia, T.
    Chinese Journal of Chemical Physics 32 (2) 175 - 181 2019/05 [Refereed]
  • Ehara, M.; Morisawa, Y.
    Molecular Spectroscopy: A Quantum Chemistry Approach Molecular Spectroscopy: A Quantum Chemistry Approach 2019
  • Endo, A.; Hatanaka, M.; Ueno, N.; Morisawa, Y.; Wakabayashi, T.
    Fizika Nizkikh Temperatur 45 (7) 807 - 815 0132-6414 2019/01 
    © 2019 Institute for Low Temperature Physics and Engineering. All rights reserved. The A-X transition of diatomic bismuth, Bi2, was revisited by laser induced fluorescence in solid Ne at 3 K. Molecular constants, i.e., vibrational frequencies of 137 cm-1 and 174 cm-1, were reproduced for the upper and lower electronic states as reported by Bondybey et al. [Chem. Phys. Lett. 76, 30 (1980)]. Two-dimensional mapping of emission spectra confirmed satellite bands in higher and lower excitation/emission energies for each of the major bands in the vibrational progression of v′-v″ (v′ = 0.5, v″ = 5-12). Based on the molecular orbital cal-culations, presence of clusters, Bi2Nen (n = 1-6), is proposed for possible carriers of the observed satellites. For the relatively large matrix shift of ∼ 67 cm-1 in solid Ne for the term energy of the A state, the diatomic bismuthis supposed to exist as a linearly coordinated cluster of Bi2Ne in the matrix.
  • Krzysztof B. Bec; Yusuke Morisawa; Kenta Kobashi; Justyna Grabska; Ichiro Tanabe; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY C AMER CHEMICAL SOC 122 (50) 28998 - 29008 1932-7447 2018/12 [Refereed]
     
    We measured the electronic spectra of graphene nanostructures (flakes and platelets) extending into the far ultraviolet (FUV) region by attenuated total reflection far- and deep-ultraviolet (ATR-FUV-DUV) spectroscopy in the region of 2.76-8.55 eV (450-145 nm). The major absorption of graphene appears in the DUV region (4.7 eV), as already reported; however, we observed a new peak in the FUV region, visible clearly in the case of flakes at 7.5-7.7 eV (165-161 nm) and less pronounced in the spectrum of the platelets at 6.6-6.7 eV (188-185 rim). Graphene flakes (thickness 1-2 nm; sub micrometers of side dimension) and nanoplatelets (thickness 6-8 nm; several micrometers of side dimension) give notably different ATR absorbance spectra in the spectral region studied. This discrepancy is reduced upon applying mechanical pressure on the samples. These observations can evidence that the morphology as well as electronic structure of graphene can be manifested in the FUV DUV region. Quantum chemical calculations were applied to several molecular models incorporating the expected principal structural features of graphene nanostructures. On the basis of the results of time-dependent density functional theory and Zerner's intermediate neglect of differential overlap (ZINDO) calculations, it was possible to consistently reproduce the experimental spectral variations in terms of both band positions and intensities. The spectral differences result from the differences in the die area, ordering and the number of layers, and structural factors which separate nanoflakes and nanoplatelets. These results provide insights into the probable origins of the spectral variability of graphene nanostructures as well as the molecular orbitals involved in a FUV pi-pi* transition of graphene nanostructures.
  • Nami Ueno; Tomonari Wakabayashi; Yusuke Morisawa
    SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY PERGAMON-ELSEVIER SCIENCE LTD 197 170 - 175 1386-1425 2018/05 [Refereed]
     
    We measured the attenuated total reflectance-far ultraviolet (ATR-FUV) spectra of poly(ethylene glycol) (PEG; average molecular weights of 200, 300, and 400) and related materials in the liquid state in the 145-200-nm wavelength region. For appropriately assigning the absorption bands, we also performed theoretical simulation of the unit-number dependent electronic spectra. The FUV spectra of PEGs contain three bands, which are assigned to the transitions between n(CH2OCH2)-3s Rydberg state (176 nm), n(CH2OCH2)-3p Rydberg state (163 nm), and n(OH)-3p Rydberg state (153 nm). Since the contribution of n(OH) decreases compared to n (CH2OCH2) with increase in the number of units, the ratios of the molar absorption coefficients, epsilon, at 153 nm relative to 163 nm, decrease. On the other hand, the ratio of epsilon at 176 nm to that at 163 nm increases with increase in the number of units, because of the difference in the number of unoccupied orbitals in the transitions. The calculated results suggest that n orbitals form two electronic bands. In the upper band, the electrons expand over the ether chain, whereas in the lower band, the electrons are localized in the terminal OH in the PEGs. (C) 2018 Elsevier B.V. All rights reserved.
  • Yusuke Morisawa; Arisa Suga
    SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY PERGAMON-ELSEVIER SCIENCE LTD 197 121 - 125 1386-1425 2018/05 [Refereed]
     
    Visible (Vis), near-infrared (NIR) and IR spectra in the 15,600-2500 cm(-1) region were measured for methanol, methanol-d(3), and t-butanol-d(9) in n-hexane to investigate effects of intermolecular interaction on absorption intensities of the fundamental and the first, second, and third overtones of their OH stretching vibrations. The relative area intensities of OH stretching bands of free and hydrogen-bonded species were plotted versus the vibrational quantum number using logarithm plots (V = 1-4) for 0.5 M methanol, 0.5 M methanol d(3), and 0.5 M t-butanol-d(9) in n-hexane. In the logarithm plots the relative intensities of free species yield a linear dependence irrespective of the solutes while those of hydrogen-bonded species deviate significantly from the linearity. The observed results suggest that the modifications in dipole moment functions of the OH bond induced by the formation of the hydrogen bondings change transient dipole moment, leading to the deviations of the dependences of relative absorption intensities on the vibrational quantum number from the linearity. (C) 2017 Elsevier B.V. All rights reserved.
  • Krzysztof B. Bec; Yusuke Morisawa; Kenta Kobashi; Justyna Grabska; Ichiro Tanabe; Erika Tanimura; Harumi Sato; Marek J. Wojcik; Yukihiro Ozaki
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS ROYAL SOC CHEMISTRY 20 (13) 8859 - 8873 1463-9076 2018/04 [Refereed]
     
    We investigated the surface (<50 nm) of poly(3-hydroxybutyrate) (PHB) and its nanocomposite with graphene by attenuated total reflection far- and deep-ultraviolet (ATR-FUV-DUV; 145-300 nm; 8.55-4.13 eV) spectroscopy and quantum mechanical calculations. The major absorption of polymers occurs in FUV and is related to Rydberg transitions. ATR-FUV-DUV spectroscopy allows for direct measurements of these transitions in the solid phase. Using ATR-FUV-DUV spectroscopy, periodic density functional theory (DFT) and time-dependent DFT (TD-DFT), we explained the origins of the FUV-DUV absorption of PHB and provided insights into structural changes of PHB which occur upon formation of a graphene nanocomposite and upon heating of the pure polymer. The structural changes cause specific and gradual spectral variations in FUV-DUV. We systematically studied the relaxation of the polymer helix and concluded that the common feature of all models of the unfolded helix lies in a specific and consistent FUV-DUV spectral signature. Relaxed structures feature a blue-shift of the major FUV transition (non-bonding molecular orbital to Rydberg 3p and to *) as compared with crystalline PHB. The FUV absorption of the relaxed structures was determined to be significantly stronger than that of the crystalline state. These results are consistent with the observed temperature-dependent spectra of the pure PHB. The simulation of the thermal expansion of the crystalline polymer by a periodic-DFT study allows us to exclude the possibility that spectral variations observed experimentally are influenced by changes in the crystalline phase. We concluded that the crystallinity of PHB at the sample surface increases with an increase in graphene content in the nanocomposite. However, it is unlikely that the polymer structure inside the crystal is affected; instead the FUV-DUV spectral variations result from changes in the polymer morphology that occur at the sample surface. The phase transition of PHB is affected by temperature and addition of graphene content. These changes are likely to be the opposite of those occurring in the bulk sample.
  • Yusuke Morisawa; Ichiro Tanabe; Yukihiro Ozaki
    Frontiers and Advances in Molecular Spectroscopy 251 - 285 2018 [Refereed]
     
    © 2018 Elsevier Inc. All rights reserved. This chapter is concerned with recent advances in far-ultraviolet (FUV) spectroscopy of liquids and solids. In the FUV region not only - and n-π but also Rydberg transitions may be observed. Using an attenuated total reflection (ATR)-FUV spectrometer, one can measure FUV spectra of almost all kinds of solid and liquid samples. The most fundamental advantage of FUV spectroscopy is that it contains unique information about the electronic transitions and structure of molecules. In this chapter principle, advantages, and instrument of FUV spectroscopy for studies of condensed matters are described first, and then ATR-FUV studies of electronic structure of organic molecules, polymers, and water are reported. To interpret their spectra quantum chemical calculations were carried out. Finally, FUV spectroscopy of inorganic semiconductor powders is discussed. ATR-FUV spectroscopy has opened a new avenue for σ chemistry.
  • Akihiro Shimizu; Shun Horiuchi; Ryutaro Hayashi; Kouichi Matsumoto; Yu Miyamoto; Yusuke Morisawa; Tomonari Wakabayashi; Jun-ichi Yoshida
    ARKIVOC ARKAT USA INC 2018 (2) 97 - 113 1551-7004 2018 [Refereed]
     
    Thiirenium ions generated and accumulated by low-temperature electrochemical oxidation of disulfides in the presence of alkynes were successfully observed by low-temperature NMR, Raman, and mass spectroscopies and were found to be stable at temperatures below -40 degrees C. The thiirenium ions showed ambident reactivity toward subsequently added nucleophiles to give either disubstituted alkenes or alkynes depending on the nature of the nucleophiles.
  • Yusuke Morisawa; Nami Ueno; Kazutaka Nishikido
    UV AND HIGHER ENERGY PHOTONICS: FROM MATERIALS TO APPLICATIONS 2018 SPIE-INT SOC OPTICAL ENGINEERING 10727 0277-786X 2018 [Refereed]
     
    Far-ultraviolet (FUV) spectroscopy gives rich information about changes in the electronic states of molecules from interactions in condensed phase. We are investigated electronic states of molecules in the condensed ionic environment such as gel electrolytes, ionic liquids, and deep eutectic solvents. To measure the FUV spectra for liquid and solid nondestructively and feasibly, attenuate total reflectance (ATR) spectroscopy were developed to measure spectra of liquid, gel and solid samples in the 140-300 nm region. In this paper, we discuss about changes by interaction due to ionic environment in the electronic state of poly (ethylene glycol) (PEG) in gel electrolytes with Li salts, and deep eutectic solvents composed of acetamide and Li salts.
  • Akifumi Ikehata; Takeyoshi Goto; Yusuke Morisawa
    APPLIED SPECTROSCOPY SAGE PUBLICATIONS INC 71 (7) 1530 - 1536 0003-7028 2017/07 [Refereed]
     
    Attenuated total reflection (ATR) spectra, which are often used in IR analysis, can be transformed into extinction and refraction spectra by Kramers-Kronig transformation (KKT) with Fresnel equations. However, it is often difficult to obtain correct optical indices due to the inherent instrumental functions. This paper proposes a simple practical method for correction of KKT with two parameters, which include all the effects of the instrumental function. In order to obtain the parameters of the instrumental function, absorption ratios of charge transfer to solvent (CTTS) transitions of aqueous iodide ions observed at 195 nm and 230 nm were used as a standard. The absorption indices calculated from the ATR spectra with the parameters correspond reasonably well to those given by the transmittance spectra not only in the UV region but also in the far-ultraviolet (FUV, 120-200 nm) region. By applying the corrected KKT to the ATR-FUV spectra of aqueous potassium halide solutions in the range of 0-2 M, correct features of the absorption spectra of KCl and KBr, whose CTTS bands are thought to be observed in FUV region, were confirmed. It is possible to use the parameters representing the instrument function as long as the instrument is not changed.
  • Ichiro Tanabe; Takeyoshi Goto; Yusuke Morisawa; Yukihiro Ozaki
    BUNSEKI KAGAKU JAPAN SOC ANALYTICAL CHEMISTRY 66 (5) 319 - 331 0525-1931 2017/05 [Refereed]
     
    Recently, spectroscopy and photonics in the far-ultraviolet (FUV) region (120 - 200 nm region) have been a matter of great attention because of rapid development of sensitive instruments in this region and an increase in the possible applications. In the present work the state-of-the-art of progress in FUV spectroscopy of the liquids and solids, which are concerned with various valence electronic transitions including sigma, n, and pi electrons, were outlined. FUV spectroscopy is rich in information about the electronic structure and transitions of a molecule, but the absorptivity is very high for liquid and solid states in the FUV region. Thus, spectral measurements for condensed matter in this region were difficult. To overcome this difficulty we introduced an attenuated total reflection (ATR) technique to the FUV region. ATR-FUV spectroscopy has paved a new avenue for condensed-matter FUV spectroscopy. This article demonstrates that FUV holds considerable promise in various fields of research from basic science, such as studies of electronic structure of molecules and those of hydrogen bonding, hydration, and adsorption of water, to material researche, such as polymers, inorganic semiconductors, and ionic liquids.
  • Yusuke Morisawa; Shin Tachibana; Akifumi Ikehata; Tao Yang; Masahiro Ehara; Yukihiro Ozaki
    ACS OMEGA AMER CHEMICAL SOC 2 (2) 618 - 625 2470-1343 2017/02 [Refereed]
     
    Intermolecular interactions between alkyl chains such as CH center dot center dot center dot HC should be reflected in the phase behavior of organic compounds. We measured the attenuated total reflectance spectra in the far-UV region (145-300 nm) of n-tetradecane (T-m = 5.9 degrees C), through both cooling and heating, from 15 to -38 degrees C, to determine its temperature dependency. The chosen temperature range, with the minimum temperature much lower than the melting point of n-tetradecane, allowed for a detailed examination of the liquid- solid phase transition. With decreasing temperature, the absorption band at 153 nm in the liquid phase becomes weaker, and new bands appear at around 200 and 230 nm. Because the observed variations in the band intensities are reversible during both cooling and heating processes and the conversion from the 153 nm band to 200 and 230 nm bands takes place at the melting temperature, we concluded that these spectral changes are caused by changes in the electronic states because of the phase change. To understand the origin of this drastic change observed experimentally, we carried out time-dependent density functional theory calculations using a model dimer structure of n-pentane and periodic density functional theory calculations of the polyethylene crystal structure. Although the simulated absorption spectra of both the optimized and crystal structures did not explain the changes observed experimentally in the absorption spectra, compressed structures were found to be a potential explanation for the experimental findings. These results suggest that an unusually compressed structure might be generated on the surface at low temperatures, and this phase change, which is reversible, is responsible for the unusual absorption observed in the attenuated total reflection-far ultraviolet spectra.
  • Yusuke Morisawa; Nami Ueno; Shin Tachibana; Masahiro Ehara; Yukihiro Ozaki
    UV AND HIGHER ENERGY PHOTONICS: FROM MATERIALS TO APPLICATIONS 2017 SPIE-INT SOC OPTICAL ENGINEERING 10351 0277-786X 2017 [Refereed]
     
    The wavelength region shorter than 200 nm, far-ultraviolet (FUV) region, is very rich in information about the electronic states and structure of a molecule. We have recently developed a totally new UV spectrometer based on attenuated total reflection (ATR) that enables us to measure spectra of liquid and solid samples in the 140-280 nm region. This paper shows the studies by the attenuated total reflection far-ultraviolet (ATR-FUV) spectroscopy. Intermolecular interactions between alkyl chains such as CH---HC should be reflected in the phase behavior of organic compounds. We measured the attenuated total reflectance spectra in the far-UV region (145-300 nm) of n-tetradecane (Tm = 5.9 degrees C) from 15 to -38 degrees C to determine its temperature dependency. With decreasing temperature, the absorption band at 153 nm in the liquid phase becomes weaker and new bands appear at around 200 and 230 nm. These results suggest that an unusually compressed structure might be generated at the surface at low temperatures, and this phase change, which is reversible, is responsible for the unusual absorption observed in the ATR-FUV spectra. We have also investigated composite polymer electrolytes (CPE). ATR-FUV spectra of CPEs composed of Poly(ethylene oxide) (PEO) and Li salt were observed and its variation of anions for the CPEs are studied.
  • Ichiro Tanabe; Yuji Kurawaki; Yusuke Morisawa; Yukihiro Ozaki
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS ROYAL SOC CHEMISTRY 18 (32) 22526 - 22530 1463-9076 2016/08 [Refereed]
     
    Electronic absorption spectra of imidazolium-based ionic liquids were studied by far- and deep-ultraviolet spectroscopy and quantum chemical calculations. The absorption spectra in the 145-300 nm region of imidazolium-based ionic liquids, [C(n)mim](+)[BF4](-) (n = 2, 4, 8) and [C(4)mim](+)[PF6](-), were recorded using our original attenuated total reflectance (ATR) system spectrometer. The obtained spectra had two definitive peaks at similar to 160 and similar to 210 nm. Depending on the number of carbon atoms in the alkyl side chain, the peak wavelength around 160 nm changed, while that around 210 nm remained at almost the same wavelength. Quantum chemical calculation results based on the time-dependent density functional theory (TD-DFT) also showed the corresponding peak shifts. In contrast, there was almost no significant difference between [C(4)mim](+)[BF4](-) and [C(4)mim](+)[PF6](-), which corresponded with our calculations. Therefore, it can be concluded that the absorption spectra in the 145-300 nm region are mainly determined by the cations when fluorine-containing anions are adopted. In addition, upon addition of organic solvent (acetonitrile) to [C(4)mim](+)[BF4](-), small peak shifts to the longer wavelength were revealed for both peaks at similar to 160 and similar to 210 nm. The peak shift in the deep-ultraviolet region (<= 200 nm) in the presence of the solvent, which indicates the change of electronic states of the ionic liquid, was experimentally observed for the first time by using the ATR spectrometer.
  • Goto, T.; Morisawa, Y.
    Encyclopedia of Spectroscopy and Spectrometry Encyclopedia of Spectroscopy and Spectrometry 2016
  • Yusuke Morisawa; Shin Tachibana; Masahiro Ehara; Yukihiro Ozaki
    UV and Higher Energy Photonics: From Materials to Applications SPIE-INT SOC OPTICAL ENGINEERING 9926 992604-(1) - 992604-(7) 0277-786X 2016 [Refereed]
     
    The wavelength region shorter than 200 nm, far-ultraviolet (FUV) region, is very rich in information about the electronic states and structure of a molecule. Since the molar absorption coefficient is very high (similar to 10(5) mol(-1) dm(3) cm(-1)) in the FUV region, the electronic states and structure mainly for gas molecules has been investigated for a long time. On the other hand, as to molecules in the condensed phase transmittance spectra could not measure because of high molecular density, and reflection spectroscopy has been used to observe spectra of solid samples in the FUV region. However, for liquid samples generally either absorption spectroscopy or specular reflection spectroscopy was difficult to observe. Accordingly, FUV spectroscopy for liquid samples has been a relatively undeveloped research area. To solve the above difficulties of FUV spectroscopy we have recently developed a totally new UV spectrometer based on attenuated total reflection (ATR) that enables us to measure spectra of liquid and solid samples in the 140-280 nm region. This paper shows the studies by the attenuated total reflection far-ultraviolet (ATR-FUV) spectroscopy. These investigations elucidate the electronic structure and electronic transition in the FUV region for molecules such as n- and branched alkanes, alcohols, ketones, amides, and nylons in the liquid or solid phase. The consistent assignments were performed with a help of quantum chemical calculation.
  • Yukihiro Ozaki; Yusuke Morisawa; Takeyoshi Goto; Ichiro Tanabe
    UV and Higher Energy Photonics: From Materials to Applications SPIE-INT SOC OPTICAL ENGINEERING 9926 992603-(1) - 992603-(6) 0277-786X 2016 [Refereed]
     
    Recently, far-ultraviolet (FUV) spectroscopy of solid and liquid states has been a matter of keen interest because it provides new possibilities for studying electronic structures and transitions of almost all kinds of molecules. It has also great potential for a variety of applications from quantitative and qualitative analysis of aqueous solutions to environmental and geographical analyses. This review describes the state-of-the-art of FUV spectroscopy; an introduction to FUV spectroscopy, the development of FUV spectrometers, investigations on electronic transitions and structure, its various applications, and future prospects.
  • Miroslaw Antoni Czarnecki; Yusuke Morisawa; Yoshisuke Futami; Yukihiro Ozaki
    CHEMICAL REVIEWS AMER CHEMICAL SOC 115 (18) 9707 - 9744 0009-2665 2015/09 [Refereed]
  • Takeyoshi Goto; Akifumi Ikehata; Yusuke Morisawa; Noboru Higashi; Yukihiro Ozaki
    BUNSEKI KAGAKU JAPAN SOC ANALYTICAL CHEMISTRY 64 (3) 173 - 184 0525-1931 2015/03 [Refereed]
     
    Far-ultraviolet (FUV, <200 nm) absorption spectroscopy provides molecular information about the electronic ground state and the excited state. Because photon energy of FUV light corresponds to various kinds of valence electronic transitions including sigma, n, and pi electron excitation and charge transfer (CT), almost all chemical compounds show characteristic FUV spectra. However, FUV spectral measurements of liquid samples are highly challenging, because the absorptivity of most liquids is very intense. We have developed an attenuated total reflection FUV spectrophotometer in order to measure the FUV spectra of liquid water and aqueous solutions. This paper introduces the FUV spectra (140-300 nm) of various aqueous solutions to describe (1) how the first electronic transition (<(A)over tilde> <- (X) over tilde )bands of water molecules in Group I, II, XIII, and lanthanoid (Ln(3+)) electrolyte solutions are associated with the hydration states of those metal cations, (2) how the protonation states of amino acids in aqueous solutions affect the electronic transition of the amino acids, and (3) the analysis of O-3 photolytic reaction in aqueous solution using a nano-sec pump-probe transient FUV spectrophotometer.
  • Takeyoshi Goto; Akifumi Ikehata; Yusuke Morisawa; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY LETTERS AMER CHEMICAL SOC 6 (6) 1022 - 1026 1948-7185 2015/03 [Refereed]
     
    The first electronic transition ((A) over tilde <- (X) over tilde) of liquid water (H2O and D2O) on an alpha-alumina substrate was studied using variable angle attenuated total reflection far-ultraviolet (VA-ATR-FUV) spectroscopy in the wavelength region 140-180 nm (8.86-6.89 eV). A variation in the penetration depth of the evanescent wave of a probe light (25-19 nrn) directly determined individual FUV spectra associated with bulk water (distance from the alumina surface >2 nm) and interfacial water (<2 nm). We found that the <(A)over tilde> <- (X) over tilde band of the interfacial water was markedly blue shifted and red-tailed relative to the bulk water. The electronic state difference of the interfacial water from the bulk water mainly arose from the hydrogen-bond structure and energy affected by the alumina surface.
  • Tomonari Wakabayashi; Yoriko Wada; Kyo Nakajima; Yusuke Morisawa; Susumu Kuma; Yuki Miyamoto; Noboru Sasao; Motohiko Yoshimura; Tohru Sato; Kentarou Kawaguchi
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 119 (11) 2644 - 2650 1089-5639 2015/03 [Refereed]
     
    Laser-induced near-infrared (NIR) emission spectra of neutral bismuth timer, Bi-3, embedded in solid neon matrixes at 3 K were recorded in a range 870-1670 nm. Using photoexcitation with low energy photons at 1064 nm, two emission band systems were newly identified by their origin bands at T-0 = 6600 and 8470 cm(-1). Accordingly, spectral assignment for three NIR emission band systems reported recently was partly revised for the one with its origin band at T-0 = 7755 cm(-1) and reconfirmed for the others at T-0 = 9625 and 11 395 cm(-1). Energy splitting by spin-orbit coupling between the pair of electronic energy levels in the ground state of bismuth trimer, Bi-3, both having a totally symmetric vibrational mode of frequency at omega"(e) = 150 cm(-1), was determined to be 1870 +/- 1.5 cm(-1). Transitions from the pair of electronically excited states, locating at T-0 = 8470 and 9625 cm(-1) above the ground state and separated by spin-orbit coupling of 1155 cm(-1), have relatively long decay constants of tau similar to 0.2 and similar to 0.1 ms, respectively.
  • Akifumi Ikehata; Yusuke Morisawa; Noboru Higashi
    Far-and Deep-Ultraviolet Spectroscopy Springer Japan 17 - 28 2015/01 [Refereed]
     
    This chapter describes recent breakthroughs in the instrumentation for far-ultraviolet (FUV) spectroscopy. The key technique is attenuated total reflection (ATR) that is frequently used in the infrared region. ATR technique decreases the absorbance of samples with strong absorptivity because of the penetration depth of the evanescent wave less than 100 nm. Therefore, ATR–FUV spectroscopy realizes the measurement of FUV spectra of samples in liquid and solid states. Some applications (in-line monitoring, characterization of polymers and time-resolved spectroscopy in sub-microsecond) are introduced in terms of instrumentation. This chapter explains not only the detail of the instruments but also the mathematical correction for ATR spectra to separate the absorption and refraction indices.
  • Yusuke Morisawa; Masahiro Ehara
    Far-and Deep-Ultraviolet Spectroscopy Springer Japan 29 - 54 2015/01 [Refereed]
     
    This chapter overviews the investigations by using the attenuated total reflection far-ultraviolet (ATR-FUV) spectroscopy. These studies elucidate the electronic structure and electronic transition of molecules in the FUV region. The target molecules or systems include n- and branched alkanes, alcohols, ketones, amides, and nylons in the liquid or solid phase. The reliable and consistent assignments were performed with the help of quantum chemical calculation protocols, namely, time-dependent density functional theory (TD-DFT) and symmetry-adapted cluster–configuration interaction (SAC-CI) calculations. The typical features in the FUV region of n- and branched alkanes, ketones, amides, and nylons were interpreted in detail. The confined Rydberg transitions were clearly probed in the studies of alkanes and ketones. The intermolecular interaction via hydrogen bonding and the polarization of the surroundings in the liquid or solid phase was analyzed for amides and nylons using the present spectroscopy.
  • Kouichi Matsumoto; Yu Miyamoto; Kazuaki Shimada; Yusuke Morisawa; Hendrik Zipse; Seiji Suga; Jun-ichi Yoshida; Shigenori Kashimura; Tomonari Wakabayashi
    CHEMICAL COMMUNICATIONS ROYAL SOC CHEMISTRY 51 (66) 13106 - 13109 1359-7345 2015 [Refereed]
     
    A low temperature in situ Raman spectroscopic method was developed for the detection of unstable intermediates in electro-organic chemistry. It was effective for monitoring the generation of ArS(ArSSAr)(+) by the electrochemical oxidation of ArSSAr (Ar = p-FC6H4) in Bu4NBF4/CH2Cl2 at 195 K. The intensity of a Raman band at 427 cm(-1), which is attributable to the S-S vibration of ArS(ArSSAr)(+), increased with an increase in the electricity until 2/3 F of the electricity was consumed, whereas decreased with a further increase in the electricity indicating the decomposition of ArS(ArSSAr)(+).
  • Yusuke Morisawa; Manaka Yasunaga; Harumi Sato; Ryoichi Fukuda; Masahiro Ehara; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY B AMER CHEMICAL SOC 118 (40) 11855 - 11861 1520-6106 2014/10 [Refereed]
     
    Attenuated total reflection far ultraviolet (ATR-FUV) spectra in the 145-260 nm region were measured for surfaces (thickness 50-200 nm) of various kinds of nylons in cast films to explore their electronic transitions in the FUV region. ATR-FUV spectra show two major bands near 150 and 200 nm in the surface condensed phase of nylons. Transmittance (Tr) spectra were also observed in particular for the analysis of valence excitations. Time-dependent density functional theory (TD-DFT/CAM-B3LYP) calculations were carried out using the model systems to provide the definitive assignments of their absorption spectra and to elucidate their peak shifts in several nylons, in particular, focusing on their crystal alignment structures and intermolecular hydrogen bondings. Two major bands of nylon films near 150 and 200 nm are characterized as sigma-Rydberg 3p and pi-pi* transitions are relatively localized at the amide group. Differences in the peak positions and intensity were found in both ATR and Tr FUV Spectra for different nylons. A red-shift of the pi-pi* amide band in the FUV spectra of nylon-6 and nylon-6/6 models in alpha form is attributed to the crystal structure pattern and the intermolecular hydrogen bondings, which result in the different delocalization character of the pi-pi* transitions and transition dipole coupling.
  • Kazutoshi Sanada; Yusuke Morisawa; Yukihiro Ozaki
    JOURNAL OF THE CERAMIC SOCIETY OF JAPAN CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI 122 (1425) 322 - 328 1882-0743 2014/05 [Refereed]
     
    The physical and optical properties of newly synthesized, environmentally friendly, highly reflective green-black (HRGB) pigments (CoO)(x)(MgO)(1-x)center dot n{(Al2O3)(y)(Fe2O3)(1-y)} (x = 0.5, y = 0.75, and n = 1) calcined at various temperatures were studied. The pigments were prepared from Fe2O3, Al(OH)(3), Mg(OH)(2), and CoCO3 by a novel modified solid solution method. The synthesis was performed at a reduced calcination temperature with lower energy consumption than the standard methods. The physical and optical properties (lower magnetization and higher total solar reflectance) of the HRGB pigments were superior to those of related pigments with the same chemical structure. Dependence of physical and spectroscopic properties of the HRGB pigments on the calcination temperature was also studied. Mixed with TiO2, a highly reflective black pigment, synthesized similarly to the HRGB pigment and possessing similar physical properties, exhibited 80% higher reflectivity than a standard black pigment similarly mixed with TiO2. (C)2014 The Ceramic Society of Japan. All rights reserved.
  • Yujing Chen; Yusuke Morisawa; Yoshisuke Futami; Miroslaw A. Czarnecki; Hai-Shui Wang; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 118 (14) 2576 - 2583 1089-5639 2014/04 [Refereed]
     
    Vibrational overtone studies primarily focus on X H stretching overtone transitions, where X is an atom like C, O, N, or S. In contrast, the studies on the C=O stretching overtones are very scattered. To advance the research in this field, we measured the fundamental, first, and second overtones of the C=O stretching vibration of acetone and 2-hexanone in n-hexane, CCl4, and CHCl3, as well as in the vapor phase using FT-IR/FT-NIR spectroscopy. Density functional theory (DFT) calculations have also been performed to help the assignment of the C=O stretching bands and to guide interpretation of the experimental results. It was found that the wavenumbers, absorption intensities, and oscillator strengths of the C=O stretching bands show marked solvent dependence. In the fundamental and the first overtone regions, the intensities of the C=O stretching vibration were found to be pronouncedly more intense than those of the C H stretching vibration. In the second overtone region, the intensities of the C H stretching vibration are comparable to those of the C=O stretching vibration. The theoretical and observed decrease in integrated intensity upon going from the fundamental to the first overtone of the C=O stretching vibration is around 50, which is significantly larger than those of the O-H, C H, and S H stretching vibration. Both the calculated and experimental results suggest that excessive weakness in the C=O stretching overtone was shown to be a result of both a low anharmonicity and a substantial reduction in the oscillator strength. These results provide new insight into our understanding of the C=O stretching vibration.
  • Yujing Chen; Hai-Shui Wang; Yusuke Morisawa; Yukihiro Ozaki
    TALANTA ELSEVIER SCIENCE BV 119 105 - 110 0039-9140 2014/02 [Refereed]
     
    For infrared (IR) spectral measurements, if a quality single-beam background spectrum with desired intensity could be obtained, the contributions from solvent and other background components could be completely suppressed and their bands would not appear in a final transmittance/absorbance spectrum. In order to achieve this ideal but difficult goal, the concept of hybrid single-beam spectrum is introduced in this paper. The hybrid single-beam spectrum (phi(h)) is defined as a mixture of two single-beam spectra (phi(b1) and phi(b2)) of the same sample but with different pathlengths (b(1) and b(2)), namely, phi(h)=alpha phi(b1)+(1 - alpha) phi(b2), where alpha(0 <= alpha <= 1) is the component factor. The properties of the hybrid spectrum have been investigated. Under conditions of b(2) > b(1) >= 0.7b(2) and A(max) <= 0.60 (A(max) is the maximum absorbance of b(2) sample in the spectral range of interest), all the synthesized hybrid spectra are free from significant distortion regardless of the component factor. Therefore, the hybrid single-beam spectrum with desired intensity can be easily obtained simply by choosing an appropriate component factor. The proposed methodology has been demonstrated experimentally by the complete removal of the interference from the atmospheric water vapor and solvent. (C) 2013 Elsevier B.V. All rights reserved.
  • Toshiaki Suzuki; Tamitake Itoh; Sanpon Vantasin; Satoshi Minami; Yasunori Kutsuma; Koji Ashida; Tada-aki Kaneko; Yusuke Morisawa; Takeshi Miura; Yukihiro Ozaki
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS ROYAL SOC CHEMISTRY 16 (37) 20236 - 20240 1463-9076 2014 [Refereed]
     
    We develop a bulk silver tip for tip-enhanced Raman scattering (TERS) and obtain TERS spectra of epitaxial graphene on the carbon face of 4H-SiC(000-1) with a high signal-to-noise ratio. Thanks to the high quality of TERS spectra we firstly find that the G band in the TERS spectra exhibits position-by-position variations in both lower wavenumber shifts and spectral broadening. The analysis of the variations reveals that the shifts and broadenings have a linear correlation between each other, indicating that the variations are induced by the position dependent local stress on graphene based on a uniaxial strain model.
  • Yusuke Morisawa; Manaka Yasunaga; Ryoichi Fukuda; Masahiro Ehara; Yukihiro Ozaki
    JOURNAL OF CHEMICAL PHYSICS AMER INST PHYSICS 139 (15) 154301  0021-9606 2013/10 [Refereed]
     
    Attenuated total reflection far-ultraviolet (ATR-FUV) spectra in the 140-260 nm region were measured for several types of liquid amides (formamide, FA; N-methylformamide, NMF; N-methylacetamide, NMA; N, N-dimethylformamide, NdMF; and N, N-dimethylacetamide, NdMA) to investigate their electronic transitions in the FUV region. The spectra were compared with the corresponding gas-phase spectra to examine the shift in the major absorption band in the 180-200 nm region going from the gas phase to the liquid phase, and it was found that the peak shift was dependent on the particular amide. FA and NMF, which exhibit intermolecular C=O center dot center dot center dot H-N hydrogen bonding, show a large shift of similar to 0.60 eV to lower energy; however, NMA, which also exhibits hydrogen bonding, shows only a small shift. In NdMF and NdMA, C=O groups seem to be coupled, which results in a small peak shift. Two types of quantum chemical calculations, time-dependent density functional theory (TD-DFT) and symmetry-adapted-cluster configuration interaction (SAC-CI) method, were performed to elucidate the origin of the shifts and the band assignments. The shift estimated by the monomer and dimer models with TD-DFT reproduced well the observed shift from the gas phase to the liquid phase. This suggests that the intermolecular hydrogen-bonding interaction significantly affects the magnitude of the shift. The many-body effects were also considered using the larger cluster models (trimer to pentamer). The energy shift calculated using SAC-CI with the monomer and the state-specific polarizable continuum model was also accurate, indicating that the nonlinear polarization effect appears to be important. As for the band assignments, it was found that though the major band can be mainly attributed to the pi-pi* transition, several types of Rydberg transitions also exist in its vicinity and mixing of orbitals with the same symmetry occurs. The number and type of Rydberg transitions in the spectra depend upon the type of amide molecules. The valence-Rydberg coupling of the pi-pi* transition is more significant than n-pi* transition, which also holds in the pure liquid phase. (C) 2013 AIP Publishing LLC.
  • Hal Suzuki; Shinya Ishii; Harumi Sato; Shigeki Yamamoto; Yusuke Morisawa; Yukihiro Ozaki; Tetsuji Uchiyama; Chiko Otani; Hiromichi Hoshina
    CHEMICAL PHYSICS LETTERS ELSEVIER 575 36 - 39 0009-2614 2013/06 [Refereed]
     
    With the aim of opening a route toward new applications of terahertz (THz) spectroscopy to studies of polymer science, the conformations and structural transitions of polycaprolactam (nylon-6) were investigated by THz spectroscopy in the alpha, gamma, pseudo-hexagonal, and amorphous phases. A Brill transition from the alpha form to the pseudo-hexagonal form was detected at 160 degrees C from a temperature variation of the peak intensity at 6.6 THz in the second-derivative spectrum of nylon-6. In the amorphous phase, a glass transition was observed at 60 degrees C, and a new anomaly was found at 110 degrees C. (C) 2013 Elsevier B. V. All rights reserved.
  • Hiromichi Hoshina; Shinya Ishii; Shigeki Yamamoto; Yusuke Morisawa; Harumi Sato; Tetsuji Uchiyama; Yukihiro Ozaki; Chiko Otani
    IEEE TRANSACTIONS ON TERAHERTZ SCIENCE AND TECHNOLOGY IEEE-INST ELECTRICAL ELECTRONICS ENGINEERS INC 3 (3) 248 - 258 2156-342X 2013/05 [Refereed]
     
    This paper reviews our recent spectroscopic study on poly(3-hydroxybutyrate) (PHB) for the terahertz (THz) frequency region. Clear differences are observed between the absorption spectra of crystalline and amorphous PHB, indicating that the higher order conformation of PHB determines the THz spectra. The THz polarization spectra are measured for a stretched PHB sample and the directions of the vibrational transition moments are determined. The spectra are found to have temperature dependences owing to which the peaks at lower frequencies shift with temperature, suggesting a large anharmonicity of the vibrational potential. To investigate low frequency vibrational modes more thoroughly, low-frequency Raman spectra are also measured for crystalline PHB. The observed vibrational modes in both THz and Raman spectra were successfully assigned by a quantum mechanical simulation of spectra with the Cartesian coordinate tensor transfer (CCT) method, which can provide realistic spectra of the PHB by considering the intermolecular interactions among polymer chains. The potential of CCT for the assignment of THz spectra is demonstrated. On the basis of these results, the structural change in PHB is studied. The isothermal crystallization of PHB is monitored with the help of THz absorption spectra. The observed spectra clearly show the crystal growth, and the crystallization rate is estimated by Avrami's model. Next, the isothermal crystallization spectra are analyzed using two-dimensional correlation spectroscopy (2DCOS). By using the synchronous and asynchronous data plots, the correlation between the absorption peaks and the temporal order of the changes in spectral intensity is determined.
  • Takeyoshi Goto; Yusuke Morisawa; Noboru Higashi; Akifumi Ikehata; Yukihiro Ozaki
    ANALYTICAL CHEMISTRY AMER CHEMICAL SOC 85 (9) 4500 - 4506 0003-2700 2013/05 [Refereed]
     
    Chemical dynamics of an ozone (O-3) pulse-photolytic reaction in aqueous solutions were studied with pump-probe transient far-ultraviolet (FUV) absorption spectroscopy. With a nanosecond pulse laser of 266 nm as pump light, transient spectra of O-3 aqueous solutions (78-480 mu M, pH 2.5-11.3) were acquired in the time range from 50 to 50 its in the wavelength region from 190 to 225 nm. The measured transient spectra were linearly decomposed into the molar absorption coefficients and the concentration-time profiles of constituted chemical components with a multivariate curve resolution method. From the dependences of the time-averaged concentrations for 20 mu s of the constituted chemicals on the initial concentration of O-3, it was found that the transient spectra involve the decomposition of O-3 and the formation of hydrogen peroxide (H2O2) and a third component that is assigned to hydroxyl radical (OH) or perhydroxyl radical (HO2). Furthermore, the pH dependence of the time-averaged concentration of the third components indicates that HO2 is more probable than OH as the third component. The time-averaged concentration ratio of each chemical component to the initial O-3 concentration depends on the pH conditions from -0.95 to -0.60 for O-3, 0.98 to 1.2 for H2O2, 0.002 to 0.29 for OH, and 0.012 to 0.069 for HO2.
  • 森澤 勇介; 後藤剛嬉; 池; 田晶文; 東昇; 尾崎幸洋
    Encyclopedia of Analytical Chemistry Wily 2013 (March) 1 - 21 2013/03 
    DOI: 10.1002/9780470027318.a9287
  • Takeyoshi Goto; Akifumi Ikehata; Yusuke Morisawa; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 117 (12) 2517 - 2528 1089-5639 2013/03 [Refereed]
     
    The electronic transitions of 20 naturally occurring amino acids in aqueous solution were studied with attenuated total reflection far-ultraviolet (ATR-FUV) spectroscopy in the region from 145 to 300 nm. From the measured ATR spectra of sample solutions, the FUV absorption spectra attributed to the amino acids were separated from the intense solvent absorption by using a modified Kramers-Kronig transformation method. The FUV absorption spectra of the amino acids reflect the protonation states of the backbone and side-chain structures. The contributions of the side chains to the spectra were also examined from the difference spectra subtracting the corresponding Gly spectrum from each spectrum. The observed spectra were compared mostly with the electronic transition studies of the molecular fragments of the amino acids in gas phase. The FUV spectra of the amino acids exhibited the intra- and intermolecular electronic interactions of the solute-solute as well as the solute-solvent, and those are essential factors to elucidate UV photochemical processes of the amino acids in aqueous solution.
  • Shigeki Yamamoto; Yusuke Morisawa; Harumi Sato; Hiromichi Hoshina; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY B AMER CHEMICAL SOC 117 (7) 2180 - 2187 1520-6106 2013/02 [Refereed]
     
    Low-frequency vibrational bands observed in the Raman and terahertz (THz) spectra in the region of 50-150 cm(-1) of crystalline powder poly-(R)-3-hydroxybutyrate (PHB) were assigned based on comparisons of the Raman and THz spectra, polarization directions of THz absorption spectra, and their congruities to quantum mechanically (QM) calculated spectra. This combination, Raman and THz spectroscopies and the QM simulations, has been rarely adopted in spite of its potential of reliable assignments of the vibrational bands. The QM simulation of a spectrum has already been popular in vibrational spectroscopies, but for low-frequency bands of polymers it is still a difficult task due to its large scales of systems and a fact that interactions among polymer chains should be considered in the calculation. In this study, the spectral calculations with the aid of the Cartesian-coordinate tensor transfer (CCT) method were applied successfully to the crystalline PHB, which include the explicit consideration of an intermolecular interaction among helical polymer chains. The agreements between the calculations and the experiments are good in both the Raman and THz spectra in terms of spectral shapes, frequencies, and intensities. A Raman active band at 79 cm(-1) was assigned to the intermolecular vibrational mode of the out-of-plane C=O + CH3 vibration. A polarization state of the corresponding far-infrared absorption band at similar to 82 cm(-1), perpendicular to the helix-elongation direction of PHB, was reproduced only under the explicit correction, which indicates that this polarized band originates from the interaction among the polymer chains. The calculation explored that the polarization direction of this band was along the a axis, which is consistent with the direction in which weak intermolecular hydrogen bonds are suggested between the C=O and CH3 groups of two parallel polymer chains. The results obtained here have confirmed sensitivity of the low-frequency vibrational bands to the weak hydrogen bonds among the polymer chains.
  • Hiromichi Hoshina; Yusuke Morisawa; Shinya Ishii; Harumi Sato; Shigeki Yamamoto; Isao Noda; Yukihiro Ozaki; Chiko Otani; Hal Suzuki
    PROCEEDINGS OF THE 2013 IEEE INTERNATIONAL CONFERENCE ON SOLID DIELECTRICS (ICSD 2013), VOLS 1 AND 2 IEEE 497 - 500 1553-5282 2013 [Refereed]
     
    Terahertz absorption spectra of poly(3-hydroxybutylate) (PHB) and nylon were measured by a terahertz time domain spectrometer and a Fourier transform far-infrared spectrometer. Clear differences were observed between the spectra of crystalline and amorphous PHB, indicating that the absorption peaks observed in the THz spectra originated in the higher-order conformation of PHB. Direction of the vibrational transition moments was obtained by the polarization spectra of stretched sample in which the crystal axis were aligned. On the basis of these results, the structural change in PHB is studied. The isothermal crystallization of PHB is monitored with the help of THz absorption spectra. The observed spectra clearly show the crystal growth, and the crystallization rate is estimated by Avrami's model. The higher order conformations of the nylon were determined by the X-ray diffraction measurement. Different spectral features among the samples were interpreted
  • Yusuke Morisawa; Shin Tachibana; Masahiro Ehara; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 116 (48) 11957 - 11964 1089-5639 2012/12 [Refereed]
     
    Attenuated total reflection far-ultraviolet (ATR-FUV) spectra containing Rydberg states of n-alkanes (CmH2m+2; m varies in the range 5-9) and branched alkanes observed in the liquid phase were investigated by quantum chemical calculations with the aim of elucidating electronic transitions from sigma orbitals of liquid n- and branched alkanes. New assignments are proposed based on the time-dependent density functional theory (TD-DFT) and symmetry-adapted cluster configuration interaction (SAC-CI) calculations, and the differences in these spectra are analyzed in detail. The FUV spectra of n-alkanes show a broad asymmetric feature near 8.3 eV. The strong band at similar to 8.3 eV shows a red shift with a significant increase in intensity as the carbon chain length increases, which is attributed to the overlapping transitions from the third (or fourth) highest occupied molecular orbitals HOMO-2 (or HOMO-3) and HOMO-1 to Rydberg 3p(y) by the TD-DFT and SAC-CI calculations. This band was previously assigned to the overlap of two peaks arising from the transition from the HOMO to 3p and from the HOMO-1 to 3s based on their term values. Although the most intense transition, T1, is from HOMO-2 for m = 5 and 6 and HOMO-3 for m varying in the range of 7-9, the shape of Kohn Sham molecular orbital for T1 is similar among the all-alkanes investigated. The theoretical result also has demonstrated that the red shift originates in both stabilization of the Rydberg 3p(y) and destabilization of the occupied orbitals. The intensity of the shoulder at 7.7 eV drastically increases in the spectra of the branched alkanes, especially for those with quaternary carbon atoms such as 2,2-dimethyl butane. This increase in intensity is caused by a reduction in symmetry in the branched alkanes, which leads the forbidden transitions to Rydberg 3s to allowed transitions, In this way, the present study has provided new insight into the existence of their Rydberg transitions and the shape of the relevant MOs of the transitions.
  • Takeyoshi Goto; Akifumi Ikehata; Yusuke Morisawa; Noboru Higashi; Yukihiro Ozaki
    INORGANIC CHEMISTRY AMER CHEMICAL SOC 51 (20) 10650 - 10656 0020-1669 2012/10 [Refereed]
     
    The effects of the lanthanoid cations (Ln(3+)) on the first electronic transition ((A) over tilde <- (X) over tilde) of liquid water were studied from the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of trivalent Ln(3+) electrolyte solutions (1 M), except Pm3+. The (A) over tilde <- (X) over tilde transition energies of the Ln(3+) electrolyte solutions show a distinct tetrad in their dependence on the number of 4f electrons of the Ln(3+) cations. For the half occupation period of the 4f electrons, the (A) over tilde <- (X) over tilde transition energies decrease from La3+ (4f(0), 8.0375 eV) to Nd3+ (4f(3), 8.0277 eV) and increase from Sm3+ (4f(5), 8.0279 eV) to Gd3+ (4f(7), 8.0374 eV). For the complete occupation period, there are two local minima at Dy3+ (4f(9), 8.0349 eV) and Yb3+ (4f(13), 8.0355 eV). The (A) over tilde <- (X) over tilde transition energies of the tetrad nodes (La3+, Gd3+, Ho3+ (4f(10)), and Lu3+ (4f(14))) increase slightly, as the nuclear charge increases in accordance with the hydration energies of the Ln(3+) cations. The energy difference (Delta E) between the (A) over tilde <- (X) over tilde transition energies and the line between La3+ and Lu3+ is largest at Nd3+ (80.5 cm(-1)) for the half occupation period and at Dy3+ (26.1 cm(-1)) and Yb3+ (24.5 cm(-1)) for the complete occupation period. The order of magnitude of Delta E is comparable to the ligand field splitting (LFS) of the ground state multiplets of Ln(3+) complexes. The observed tetrad trend of the (A) over tilde <- (X) over tilde transition energies of the Ln(3+) electrolyte solutions across the 4f period reflects the hydration energies of the Ln(3+) cations and the LFS induced by water ligands.
  • Yusuke Morisawa; Shin Tachibana; Manaka Yasunaga; Motoki Mitsuoka; Harumi Sato; Akifumi Ikehata; Noboru Higashi; Yukihiro Ozaki
    BUNSEKI KAGAKU JAPAN SOC ANALYTICAL CHEMISTRY 61 (7) 591 - 603 0525-1931 2012/07 [Refereed]
     
    Spectroscopic studies in the far-UV (FUV) region (120-200 nm) are very attractive for both basic sciences and applications, since various kinds of electronic transitions are observed in the region. However, because of very large absorption coefficients, full-scale FUV spectra for liquids and solids could not be measured easily. We have recently developed a totally new FUV spectrometer based on attenuated total reflection (ATR) that enables us to measure the full-scale spectra of liquid and solid samples in the 140-200 nm region. In this paper, at first we outline the characteristics and advantages of the FUV spectroscopy, and then discuss our studies on the development of an ATR-FUV spectrometer and its applications to analytical chemistry. At the end, we introduce our newly developing time-resolved ATR-FUV spectrometer.
  • Yoriko Wada; Yusuke Morisawa; Tomonari Wakabayashi
    CHEMICAL PHYSICS LETTERS ELSEVIER SCIENCE BV 541 54 - 59 0009-2614 2012/07 [Refereed]
     
    A series of molecular complexes, C2nH2I6 (n = 5-9), formed from size-selected hydrogen-end-capped polyyne, H(C C)(n)H, and iodine molecules was characterized by UV-vis and IR absorption spectroscopy for elucidating location and geometry of iodine atoms in the complex. The IR lines for the CH-stretching sigma(u) fundamental at 3305 cm (1) and CH-bending pi(u) fundamental at 625 cm (1) for C2nH2 (n = 5-7) in CCl4 were red-shifted by 220 and 15 cm (1), respectively, for its complex of C2nH2I6. A few lines were intensified in the low-frequency region of 850-1450 cm (1) for CC-stretching sigma(u) modes of polyynes in the complex. (C) 2012 Elsevier B. V. All rights reserved.
  • Yusuke Morisawa; Noboru Higashi; Kyoko Takaba; Naomi Kariyama; Takeyoshi Goto; Akifumi Ikehata; Yukihiro Ozaki
    REVIEW OF SCIENTIFIC INSTRUMENTS AMER INST PHYSICS 83 (7) 073103  0034-6748 2012/07 [Refereed]
     
    A far-ultraviolet transient absorption spectrometer based on time-resolved attenuated total reflectance (ATR) has been developed and tested for aqueous solutions of phenol and tryptophan in the region 170-185 nm. In this region, a stable tunable laser was not available, and therefore, white light from a laser-driven Xe lamp source was used. The time resolution, which was determined by the time response of a continuous light detector, was 40 ns. A new ATR cell where a sample liquid is exchanged continuously by a flow system was designed to reduce efficiently the stray light from the excitation light. We have tested the performance of the instrument by using aqueous solutions of phenol and tryptophan, whose photochemistry is already well known. Phenol and tryptophan have very strong absorptions due to a pi-pi* transition near 180 nm. Even for dilute solutions (10(-3) mol dm(-3)), we could observe decreases in their concentrations due to photochemistry that occurred upon their irradiation with a fourth harmonic generation laser pulse produced by an Nd:YAG laser. The sensitivity of the spectrometer was about 10(-4) abs, which corresponded to a concentration variation of 10(-3) mol dm(-3) for phenol and tryptophan. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4732846]
  • Yoshisuke Futami; Yusuke Morisawa; Yasushi Ozaki; Yoshiaki Hamada; Marek J. Wojcik; Yukihiro Ozaki
    JOURNAL OF MOLECULAR STRUCTURE ELSEVIER SCIENCE BV 1018 102 - 106 0022-2860 2012/06 [Refereed]
     
    Vibrational potentials and dipole moment functions of HF molecule in solutions have been calculated as a function of dielectric constant by using the self-consistent reaction field (SCRF)/isodensity surface polarized continuum model (IPCM) calculation. We have selected HF molecule as the simplest polar molecule. The wavenumbers and absorption intensities of the fundamental and the first, second and third overtones of H-F stretching mode have been calculated as a function of dielectric constant. The SCRF/IPCM model calculations have revealed that the vibrational potential and dipole moment function of HF molecule vary continuously with a change in the dielectric constant of the solvent. The calculations were carried out at B3LYP/6-311++G(3df,3pd) and CCSD/aug-cc-pVQZ levels. It has also been found that the absorption intensities of the fundamental increase with the increase of the dielectric constant smoothly but those of the first, second and third overtones do not increase continuously. Moreover, the B3LYP and CCSD levels yielded significantly different results in the dependence of absorption intensities on the dielectric constant. (C) 2012 Elsevier B.V. All rights reserved.
  • Yusuke Morisawa; Satoshi Nomura; Kazutoshi Sanada; Yukihiro Ozaki
    APPLIED SPECTROSCOPY SAGE PUBLICATIONS INC 66 (6) 665 - 672 0003-7028 2012/06 [Refereed]
     
    This paper demonstrates the potential of near-infrared (NIR) electronic spectroscopy in nondestructive monitoring of a chemical reaction of inorganic functional material. For this purpose NIR spectra in the 12000-4000 cm(-1) region were measured for high reflective green-black (HRGB) pigments (Co0.5Mg0.5Fe0.5Al1.5O4) calcined at 1000, 1100, and 1200 degrees C and pigments with the same components as HRGB but calcined at different temperatures (500-900 degrees C) (hereafter, called "Pigments A"). NIR spectra of their components such as Co3O4, MgO, Fe2O3, and Al2O3 were also measured. The NIR spectra of Pigments A show two major broad bands. One arises from a (4)A(2 ->)(4)T(1) (T-h) d-d transition of Co(II) in the 9000-6000 cm(-1) region. The other band in the 12000-9000 cm(-1) region is assigned to a foot of the charge-transfer (CT) hand of Fe2O3. The Co(II) band contains three component bands that are characteristic of a spinel structure. A shoulder arising from (A(1-x)B(x))(Th)(A(x)B(2-x))O-Oh(4) (A Co, Mg, B Fe, Al; inverse spinel structure) emerges near 5900 cm(-1) in the spectra of Pigments A calcined in the temperature range of 709-900 degrees C, indicating that the Pigments A calcined in this temperature range assume an inverse spinel structure. When the calcination temperature is above 1000 degrees C, the final product, HRGB, is produced. This is confirmed from the fact that HRGB shows peaks characteristic of a spinel structure that have different wavenumbers front those of the corresponding peaks of Pigments A. Wide-angle X-ray diffraction (WAXD) patterns were also measured for HRGB, Pigments A, and their components. Based on the NIR and WAXD data we investigated calcination-temperature dependent crystal structural changes of the components. We also developed partial least squares (PLS) calibration models for the 9000-6000 cm(-1) region of the NIR spectra of HRGB and Pigments A. The score plot of latent variable (LV) 2 of the calibration model for calcination temperature demonstrates clearly the existence of an intermediate of the calcination reaction, which may be (A(1-x)B(x))(Th)(A(x)B(2-x))O-Oh(4) (A Co, Mg, B Fe, Al).
  • Takeyoshi Goto; Akifumi Ikehata; Yusuke Morisawa; Noboru Higashi; Yukihiro Ozaki
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS ROYAL SOC CHEMISTRY 14 (22) 8097 - 8104 1463-9076 2012 [Refereed]
     
    The first electronic transition ((A) over tilde <- (X) over tilde) of liquid water was studied from the perspective of the hydration of cations by analyzing the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of the Group I, II, and XIII metal nitrate electrolyte solutions. The (A) over tilde <- (X) over tilde transition energies of 1 M electrolyte solutions are higher (Li+: 8.024 eV and Cs+: 8.013 eV) than that of pure water (8.010 eV) and linearly correlate with the Gibbs energies of hydration of the cations. The increases in the (A) over tilde <- (X) over tilde transition energies are mostly attributable to the hydrogen bond formation energies of water molecules in the ground state induced by the presence of the cations. The deviation from the linear relation was observed for the high charge density cations, H+, Li+, and Be2+, which reflects that the electronic energies in the excited states are also perturbed. Quantum chemical calculations show that the (A) over tilde <- (X) over tilde transition energies of the water-cation complexes depend on the hydration structures of the cations. The calculated (A) over tilde <- (X) over tilde transition energies of the water molecules hydrating high charge density cations spread more widely than those of the low charge density cations. The calculated transition energy spreads of the water-cation complexes directly correlate with the widths of the (A) over tilde <- (X) over tilde transition bands measured by ATR-FUV spectroscopy.
  • Hiromichi Hoshina; Shinya Ishii; Yusuke Morisawa; Harumi Sato; Isao Noda; Yukihiro Ozaki; Chiko Otani
    APPLIED PHYSICS LETTERS AMER INST PHYSICS 100 (1) 011907/1 - 011907/3 0003-6951 2012/01 [Refereed]
     
    The isothermal crystallization of poly(3-hydroxybutylate) (PHB) was studied by monitoring the temporal evolution of terahertz absorption spectra in conjunction with spectral analysis using two-dimensional correlation spectroscopy. Correlation between the absorption peaks and the sequential order of the changes in spectral intensity extracted from synchronous and asynchronous plots indicated that crystallization of PHB at 90 degrees C is a two step process, in which C-H center dot center dot center dot O=C hydrogen bonds are initially formed before well-defined crystal structures are established. (C) 2012 American Institute of Physics. [doi:10.1063/1.3673847]
  • Yukihiro Ozaki; Yusuke Morisawa; Akifumi Ikehata; Noboru Higashi
    APPLIED SPECTROSCOPY SOC APPLIED SPECTROSCOPY 66 (1) 1 - 25 0003-7028 2012/01 [Refereed]
     
    Ultraviolet (UV) spectroscopy has long been used together with visible (Vis) spectroscopy to investigate electronic transitions of a molecule. Most studies of the electronic structure of molecules using UV spectroscopy have been carried out in the 190-380 nm region because commercial UV-Vis spectrometers are available only for that region. The wavelength region shorter than 190 nm is also very rich in information about the electronic states and structure of a molecule, but the absorptivity is very high in this region, and thus, this region has been employed to investigate mainly the electronic states and structure of gas molecules. Because condensed-phase materials with high molecular density do not transmit much light in the shorter wavelength region of the UV, reflection spectroscopy has been used to observe spectra of solid samples in the wavelength region shorter than 190 nm. However, for liquid samples one cannot generally use either absorption spectroscopy or specular reflection spectroscopy. Accordingly, UV spectroscopy in this region for liquid samples has been a relatively undeveloped research area. To solve the above difficulties of UV spectroscopy in the wavelength region shorter than 190 nm we have recently developed a totally new UV spectrometer based on attenuated total reflection (ATR) that enables us to measure spectra of liquid and solid samples in the 140-280 nm region. We will show that spectroscopy in the wavelength region shorter than 190 nm holds considerable promise not only in basic science but also in applications such as qualitative and quantitative analysis, on-line monitoring, environmental geochemical analysis, and surface analysis. The purpose of the present review paper is to report recent progress in UV spectroscopy of solid and liquid phases in the 140-280 nm region. In this review, we refer to the 120-200 nm region to as the far-UV (FUV) region. The term "vacuum UV region" is no longer appropriate for the 120-200 nm region because most recent spectrometers used in this region are not evacuated but instead incorporate a nitrogen purge. This review consists of eight parts: (1) introduction to FUV spectroscopy, (2) brief history of FUV spectroscopy, (3) development of new FUV spectrometers, (4) FUV studies of liquid water and aqueous solutions, (5) FUV spectra of organic molecules in the liquid states, (6) band assignments by quantum chemical calculations, (7) potential applications of FUV spectroscopy in liquid and solid states; and (8) future prospects of FUV spectroscopy.
  • Takayuki Gonjo; Yoshisuke Futami; Yusuke Morisawa; Marek J. Wojcik; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 115 (35) 9845 - 9853 1089-5639 2011/09 [Refereed]
     
    Visible, near-infrared (NIR) and IR spectra in the 15600-2500 cm(-1) region were measured for phenol and 2,6-difluorophenol, 2,6-dichlorophenol, and 2,6-dibromophenol in n-hexane, CCl(4), CHCl(3) and CH(2)Cl(2) to study hydrogen bonding effects and solvent dependences of wavenumbers and absorption intensities of the fundamental and the first, second, and third overtones of OH stretching vibrations. A band shift of the OH stretching vibrations from a gas state to a solution state (solvent shift) was plotted versus vibrational quantum number (v = 0, 1, 2 and 3), and it was found that there is a linear relation between the solvent shift and the vibrational quantum number. The slope of solvent shift decreases in the order of phenol, 2,6-difluorophenol and 2,6-dichlorophenol. For all of the solute molecules, the slope becomes larger with the increase in the dielectric constant of the solvents. The relative intensities of the OH stretching vibrations of phenol in CCl(4), CHCl(3), and CH(2)Cl(2) against the intensity of the corresponding OH vibration in n-hexane increase in the fundamental and the second overtone but decrease in the first and third overtones; the relative intensities show so-called "parity". The parity is more prominent for phenol that has an intermolecular hydrogen bonding than for 2,6-dihalogenated phenols that have an intramolecular hydrogen bond. These observations suggest that the intermolecular hydrogen bond between the OH group and the Cl atom plays a key role for the parity and that the intermolecular interaction between the solutes and the solvents (solvent effects) does not have a significant role in the parity.
  • Motoki Mitsuoka; Hideyuki Shinzawa; Yusuke Morisawa; Naomi Kariyama; Noboru Higashi; Motohiro Tsuboi; Yukihiro Ozaki
    ANALYTICAL SCIENCES JAPAN SOC ANALYTICAL CHEMISTRY 27 (2) 177 - 182 0910-6340 2011/02 [Refereed]
     
    Far-ultraviolet (FUV) spectra in the 190 - 300 nm region were measured for spring water in Awaji-Akashi area, Tamba area and Rokko-Arima area in Hyogo Prefecture, Japan, these areas have quite different geology features. The spectra of the spring water in the Awaji-Akashi area can be divided into two groups: the spring water samples containing large amounts of NO3- and/or Cl-, and those containing only small amounts of NO3- and Cl-. The former shows a saturated band below 190 nm due to NO3- and/or Cl-. These two types of spectra correspond to different lithological areas: sedimentary lithology near the sea shore containing many ions in the seawater and gravitic lithology far from the sea side, in the Awaji-Akashi area. The spring water from the Tamba area, which is far from the sea, contains relatively small amounts of NO3- and Cl-; it does not yield a strong band in the region observed. The FUV spectra of three of four kinds of spring water samples in the Arima Hotspring show characteristic spectral patterns. They are quite different from the spectra of the spring water samples of the Rokko area. Calibration models were developed for NO3-, Cl-, SO42-, Na+, and Mg2+ in the nine kinds of spring water collected in the Awaji-Akashi area, Tamba, and Rokko-Arima area by using univariate analysis of the first derivative spectra and the actual values obtained by ion chromatography. NO3- yields the best results: correlation coefficient of 0.999 and standard deviation of 0.09 ppm with the wavelength of 212 nm. Cl- also gives good results: correlation coefficient of 0.993 and standard deviation of 0.5 ppm with the wavelength of 192 nm.
  • Yusuke Morisawa; Akifumi Ikehata; Noboru Higashi; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 115 (5) 562 - 568 1089-5639 2011/02 [Refereed]
     
    Far-ultraviolet (FUV) spectra in the 8.55-6.20 eV (145-200 inn) region were measured for several kinds of ketones in the liquid phase to investigate low-n Rydberg transitions using a uniquely developed technique of attenuated total reflection (AIR) FUV spectrometry. Assignments of the transitions are attempted for absorptions in this region by comparing the spectra for the liquid phase with those for the gas phase and ab initio calculations at the equation-of-motion coupled cluster theory with single and double substitutions at the aug-cc-pVDZ level. The transition from a nonbonding electron (n) to the 3s Rydberg orbital was found at around 6.7 eV for all investigated liquid ketones. Another intense band also appeared in the higher-energy region (ca. 8.5 eV) for all the ketones. A significant shoulder was found at around 7.4 eV for branched ketones. This shoulder band near 7.4 eV was assigned to the n-3p Rydberg transition. Band broadening and higher energy shifts were observed in the spectra of the liquid phase ketones in comparison with those of the gas phase ketones.
  • Shin Tachibana; Yusuke Morisawa; Akifumi Ikehata; Harumi Sato; Noboru Higashi; Yukihiro Ozaki
    APPLIED SPECTROSCOPY SAGE PUBLICATIONS INC 65 (2) 221 - 226 0003-7028 2011/02 [Refereed]
     
    Far-ultraviolet (FUV) spectra of n-alkanes (n = 5-14) and branched alkanes were measured in their liquid state by using a newly developed attenuated total reflection (ATR)-FUV spectrometer to investigate spectra structure relationship in the FUV region. The n-alkanes show a broad band near 8.3 eV and a weak shoulder near 7.7 eV. The 8.3 eV band shows a lower energy shift with a significant intensity increase with the increase in the length of alkyl chain. We have assigned the 8.3 eV band to the overlap of two bands due to the transition from the highest occupied molecular orbital (HOMO) to 3p and that from the HOMO-1 to 3s based on the observation that the peak energy of the 8.3 eV band of the n-alkanes is proportional to the first ionization energy. The 7.7 eV shoulder may be due to the transition from HOMO to 3s. The intensity of the 7.7 eV band increases markedly in the order n-alkanes without branch, with tertiary, and with quaternary carbon atoms. It is very likely that the forbidden transition from HOMO to 3s becomes allowed by the large decrease in symmetry upon going from the n-alkanes to the branched ones with the quaternary carbon, respectively.
  • Akifumi Ikehata; Takeyoshi Goto; Yusuke Morisawa; Noboru Higashi; Yukihiro Ozaki
    BUNSEKI KAGAKU JAPAN SOC ANALYTICAL CHEMISTRY 60 (1) 19 - 31 0525-1931 2011/01 [Refereed]
     
    In the far ultraviolet (FUV) region (120-200 nm), absorption bands due to transitions of outer orbital electrons have been observed. These absorption coefficients are so large that the uses of FUV spectroscopy had been limited involving applications to gases and reflectance on solid surfaces. We developed FUV spectroscopy method designed for the purpose of measuring of liquid by using attenuated total reflection (ATR) with nitrogen gas purge. The ATR-FUV spectrometer reveals the features of the FUV spectra of liquid samples. The first electronic transition band of water, which shows systematic change with the state of hydrogen bonding, had become a good candidate of this system. This paper describes the ATR-FUV analysis of aqueous solutions and the related basic properties of the UV and FUV spectra of water.
  • Hiromichi Hoshina; Yusuke Morisawa; Harumi Sato; Hiroaki Minamide; Isao Noda; Yukihiro Ozaki; Chiko Otani
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS ROYAL SOC CHEMISTRY 13 (20) 9173 - 9179 1463-9076 2011 [Refereed]
     
    Temperature-dependent terahertz (THz) absorption spectra of poly(3-hydroxyalkanoate)s (PHAs) were measured by using a Fourier transform far-infrared (FT-FIR) spectrometer and a THz time-domain spectrometer over a temperature range of 10 K to 465 K with a liquid helium cryostat and a heating cell. Clear differences were observed between the spectra of crystalline and amorphous polyhydroxybutyrate (PHB), indicating that the absorption peaks observed in the THz spectra originated in the higher-order conformation of PHB. The polarization spectra of a stretched PHB sample were measured, and the direction of the vibrational transition moment was determined. The temperature dependences of the spectra reveal frequency shifts and broadening of the absorption peaks with temperature, suggesting large anharmonicity of the vibrational potential. The temperature shift behaviour is quite different in each transition. Some of the transitions show a blue shift, which cannot be explained by a simple anharmonic potential model. Frequency shifts of the peaks were mainly observed below 10 THz, which suggests a large anharmonicity of the vibrational potential at lower frequencies.
  • Akifumi Ikehata; Motoki Mitsuoka; Yusuke Morisawa; Naomi Kariyama; Noboru Higashi; Yukihiro Ozaki
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 114 (32) 8319 - 8322 1089-5639 2010/08 [Refereed]
     
    The effect of cations (Li(+), Na(+), K(+), Rb(+), and Cs(+)) on the first electronic transition ((A) over tilde <- (X) over tilde) of liquid water was investigated by attenuated total reflection far ultraviolet spectroscopy. To negate the effect of anions, aqueous solutions of 1 M alkali metal nitrates and bromides were compared at a temperature of 25 degrees C. It is found that the peak energy of the (A) over tilde <- (X) over tilde band of water, which shows a marked red shift with decreasing hydrogen-bond strength, decreases with increasing cation size. The peak energies of the (A) over tilde <- (X) over tilde band can be approximated by a linear function of the inverse of the ionic radii of the alkali metal cations, which indicates (according to the Born equation) that the first electronic transition of water is characterized by the solvation energy of the cations.
  • Hiromichi Hoshina; Yusuke Morisawa; Harumi Sato; Akitsugu Kamiya; Isao Noda; Yukihiro Ozaki; Chiko Otani
    APPLIED PHYSICS LETTERS AMER INST PHYSICS 96 (10) 101904  0003-6951 2010/03 [Refereed]
     
    Terahertz absorption spectra of poly (3-hydroxyalkanoates) with different conformations were measured by using a terahertz time domain spectrometer. Sharp absorption peaks were observed in the spectrum of crystalline samples. The orientation direction of the transition dipole moment was investigated by the polarization spectra. The peak at 2.92 THz was assigned to a vibration of helical structure along the fiber axis, and the peak at 2.49 THz was attributed to a vibration due to the hydrogen bonding between helix structures. The temperature dependence of the spectra reflects the change in the hydrogen bonding distance and melting process of the crystalline structure. (C) 2010 American Institute of Physics. [doi:10.1063/1.3358146]
  • Yusuke Morisawa; Akifumi Ikehata; Noboru Higashi; Yukihiro Ozaki
    CHEMICAL PHYSICS LETTERS ELSEVIER SCIENCE BV 476 (4-6) 205 - 208 0009-2614 2009/07 [Refereed]
     
    Absorption bands near 155 nm due to electronic transitions of CH3OH, CH3OD, CD3OH and CD3OD in a liquid phase were observed by using a uniquely designed attenuated total reflectance-far ultraviolet (ATR-FUV) spectrometer. Their transmittance spectra were also measured for the absorption tail region of 190-220 nm. Isotope effects were found in the peak maxima and tail structures of these bands. The ATR-FUV and transmittance spectra reveal that the lowest electronic states of CH3OH and the deuterated species in the liquid phase shift to higher energy from those in the gas phase. (C) 2009 Elsevier B. V. All rights reserved.
  • Yusuke Morisawa; Yuri A. Dyakov; Chien-Ming Tseng; Y. T. Lee; Chi-Kung Ni
    JOURNAL OF PHYSICAL CHEMISTRY A AMER CHEMICAL SOC 113 (1) 97 - 102 1089-5639 2009/01 [Refereed]
     
    Photodissociation of 2,5-dihydroxyacetophenone (DHAP), an important matrix compound in matrix-assisted laser desorption/ionization (MALDI), was studied in a molecular beam at 193 nm using multimass ion imaging techniques. Two major dissociation channels were observed, including (1) C6H3(OH)(2)COCH3 -> OC6H3(OH)COCH3 + H and (2) C6H3(OH)(2)COCH3 -> C6H3(OH)(2) + COCH3. The minor channels include C6H(OH)(2)COCH3 -> C6H3(OH)(2)CO + CH3 and/or C6H3(OH)(2)COCH3 - C6H3(OH)(2) + CO + CH3. The photofragment translational energy distribution suggests that reaction I occurs at an excited state in which the potential along the O-H bond distance is repulsive. Comparison to the branching ratios from RRKM calculations suggests that reaction 2 does not occur at either the ground state or the triplet state or that if it does occur at one of these states it must not follow the RRKM-model. A comparison to the photodissociation dynamics of acetophenone and phenol and its derivatives was made.
  • Yusuke Morisawa; Mizuho Fushitani; Yoshiyasu Kato; Hiromichi Hoshina; Zenzo Simizu; Shiori Watanabe; Yuki Miyamoto; Yasuko Kasai; Kentarou Kawaguchi; Takamasa Momose
    ASTROPHYSICAL JOURNAL IOP PUBLISHING LTD 642 (2) 954 - 965 0004-637X 2006/05 [Refereed]
     
    The ortho-to-para nuclear spin ratio of cyclopropenylidene ( cyclic C3H2) in TMC-1 cores was investigated using the 45 m radio telescope at Nobeyama Radio Observatory. We have observed four ortho lines (J(KaKc) = 2(12) - 1(01), 3(12) - 3(03), 3(21) - 3(12), and 3(30) - 3(21)) and four para lines (J(KaKc) 2(02) - 1(11), 2(11) - 2(02), 2(20) - 2(11), and 3(22) - 3(13)) of cyclic C3H2 in six cores in TMC-1. A statistical equilibrium analysis of the observed intensities revealed apparent correlation between the ortho-to-para ratio of cyclic C3H2 and chemical evolution of the molecular cloud; the ortho-to-para ratio in younger cores is less than 2, while that in older cores is close to the statistical ratio of 3. A simple chemical model calculation indicates that the correlation is ascribed to the conservation of nuclear spin angular momenta in chemical reactions relevant to the production, destruction, and reproduction of cyclic C3H2. Since cyclic C3H2 has been observed in a variety of sources, the ortho-to-para ratio of cyclic C3H2 may be a useful probe of chemical evolution of molecular clouds.
  • Y Morisawa; H Hoshina; Y Kato; Z Simizu; S Kuma; N Sogoshi; M Fushitani; S Watanabe; Y Miyamoto; T Momose; Y Kasai; K Kawaguchi
    PUBLICATIONS OF THE ASTRONOMICAL SOCIETY OF JAPAN OXFORD UNIV PRESS 57 (2) 325 - 334 0004-6264 2005/04 [Refereed]
     
    Despite several suggestions concerning the existence of negatively charged molecules and negative atomic ions in molecular clouds, few attempts have been made to search for negative ions in molecular clouds. In the present study, we extensively searched for three negative molecular ions (CCH-, NCO-, and NCS-) in a dark cloud, L134N, using the Nobeyama 45-m radio telescope. The three negative ions are molecules whose rotational constants have been reported based on laboratory experiments. After a long accumulation, a trace amount of an unidentified emission line was detected at a frequency close to the theoretical prediction of the J = 1-0 transition of CCH-. If this unidentified line is attributable to CCH-, the observed emission intensity would provide an estimation of the column density of CCH- in L134N to be 1.0 x 10(11) cm(-2), which corresponds to a fractional abundance of 5 x 10(-12) relative to hydrogen. However, our recent observation using the IRAM 30-m telescope did not reproduce the J = 1-0 signal, nor detect any trace of the J = 2-1 transition. Thus, the identification of CCH- in L134N is not yet confirmed. As for other ions, signals of neither NCO- nor NCS- were detected in L134N. Although we also searched for the three negative ions in a translucent cloud, CB228, and a star-forming region, SgrB2, no signals were detected. The upper limit abundances of the ions in these clouds are discussed limit abundances of the ions in these clouds are discussed.
  • H Hoshina; Y Kato; Y Morisawa; T Wakabayashi; T Momose
    CHEMICAL PHYSICS ELSEVIER SCIENCE BV 300 (1-3) 69 - 77 0301-0104 2004/05 [Refereed]
     
    This paper presents the UV and IR absorption spectroscopy of small carbon molecules of C-3 observed using a high-resolution Fourier-transform spectrometer. The C-3 molecules were produced by irradiation of dimers or larger clusters of acetylene with an ArF laser (lambda = 193 nm). Sharp UV absorption features with multiple structures were observed in the (A) over tilde (1)Pi(u) <-- (X) over tilde (1)Sigma(g)(+) electronic transition of C-3. The sharp UV absorption demonstrates the potential of solid para-hydrogen as a matrix for high-resolution spectroscopy of UV-vis electronic transitions. (C) 2004 Elsevier B.V. All rights reserved.

Books etc

  • Marek J. Wójcik; Yukihiro Ozaki (ContributorChapter 9(p.p. 233-260), Chapter14(p.p. 409-433))Wiley‐VCH GmbH 2022/12 9783527349722 
    Chapter 9 Hydrogen Bonding from Perspective of Overtones and Combination Modes: Near-Infrared Spectroscopic Study Summary This chapter is dedicated to investigation of hydrogen bonding and various manifestations of this phenomenon by near-infrared (NIR) spectroscopy. This technique offers some benefits for hydrogen bonding studies, as compared with the IR spectroscopy. The free and weakly bonded OH or NH groups are more pronounced in the NIR spectra as compared with bonded groups, while in the IR spectra an opposite situation occurs. Hence, many aspects of the hydrogen bonding are better seen in the NIR spectra. However, a complementary application of the IR and NIR spectroscopy guided by theoretical calculations provides more comprehensive information on the hydrogen bonding, anharmonicity, vibrational potential, and dipole moments. In this chapter are shown examples of application of NIR spectroscopy for investigation of molecular structure and interactions in water, 1-alcohols, acetonitriles, alcohol/alcohol and alcohol/alkanes binary mixtures, poly(3-hydroxybutyrate), 2,6-dihalogenophenols, and pyrrole. CHAPTER 13 ATR -Far-Ultraviolet Spectroscopy Holds Unique Advantages for Investigating Hydrogen Bondings and Intermolecular Interactions of Molecules in Condensed Phase Summary This chapter is concerned with ATR-far-Ultraviolet (FUV) spectroscopy study of hydrogen bondings. ATR-FUV spectroscopy is relatively new electronic spectroscopy for condensed phase and allows to investigate electronic states of almost all kinds of molecules. It holds unique advantage for investigating hydrogen bondings and intermolecular interactions of molecules in condensed phase. This chapter describe several interesting examples of ATR-FUV studies of hydrogen bondings and intermolecular interactions.
  • 小澤 岳昌; 北森 武彦; 中村 洋(東京理科大学名誉教授); 藤浪 眞紀; 宮村 一夫; 石丸 洋一郎; 浦野 泰照; 加地 範匡; 坂 真智子; 鈴木 茂; 瀬藤 光利; 宗林 由樹; 馬場 嘉信; 船津 公人; 本田 暁紀; 末永 智一; 宮野 博; 本山 晃 (Contributor原理編 2章 2 ラマン分光)エヌ・ティー・エス 2022/01 4860437373 973
  • Yukihiro Ozaki, Harumi Sato (Contributor6. Far Ultraviolet Spectroscopy for Polymers)Wiley-VCH 2022/01 3527348336 496 27 
    An insightful exploration of cutting-edge spectroscopic techniques in polymer characterization In Spectroscopic Techniques for Polymer Characterization: Methods, Instrumentation, Applications, a team of distinguished chemists delivers a comprehensive exploration of the vast potential of spectroscopic characterization techniques in polymer research. The book offers a concise outline of the principles, advantages, instrumentation, experimental techniques, and noteworthy applications of cutting-edge spectroscopy. Covering a wide range of polymers, from nylon to complex polymeric nanocomposites, the author presents recent developments in polymer science to polymer, analytical, and material chemists, assisting them in keeping track of the progress in modern spectroscopy. Spectroscopic Techniques for Polymer Characterization contains contributions from pioneers in modern spectroscopic techniques from around the world. The included materials bridge the gap between spectroscopists, polymer scientists, and engineers in academia and industry. The book also offers: A thorough introduction to the progress in spectroscopic techniques, including polymer spectroscopy and near-infrared spectroscopy Comprehensive explorations of topical polymers studied by spectroscopy, including polymer thin films, fluoropolymers, polymer solutions, conductive polymers Practical discussions of infrared imaging, near-infrared imaging, two-dimensional correlation spectroscopy, and far-ultraviolet spectroscopy In-depth examinations of spectroscopic studies of weak hydrogen bonding in polymers Spectroscopic Techniques for Polymer Characterization: Methods, Instrumentation, Applications is a must-read reference for polymer, analytical, and physical chemists, as well as materials scientists and spectroscopists seeking a one-stop resource for polymer characterization using spectroscopic analyses.
  • 築山 光一; 星野 翔麻 (Contributor2.5 遠紫外領域における反射分光)講談社 2021/08 4065238056 336 17 
    本書は分光法の基本中の基本である吸収分光法・蛍光分光法と、使用頻度の割に解説書が少ない円偏光分光法(旋光度測定と円二色性測定)に加え、最先端のレーザー分光法までを1冊にまとめた、紫外・可視領域の分光法に関する必携の書籍です。
  • 尾崎, 幸洋; Huck, Christian; 土川, 覚; Engelsen, Søren Balling (Contributor(Principles and Characteristics of NIR Spectroscopy andSpectral Analysis in the NIR Spectroscopy))Springer Nature Singapore 2020/11 9811586470 601
  • 川﨑, 英也; 中原, 佳夫; 長谷川, 健 (Contributor4 可視・紫外分光法蛍光)化学同人 2020/02 4759820213 180
  • 尾崎, 幸洋; Wójcik, Marek Januz; Popp, Jürgen (Contributor4 Theoretical and Experimental Molecular Spectroscopy of the Far-Ultraviolet Region)Wiley-VCH 2019/09 3527344616 640
  • Jaan Laane Ed (ContributorAdvances in Far-Ultraviolet Spectroscopy in the Solid and Liquid State)Elsevier Science 2017/11 0128112204 788
  • Yukihiro Ozaki; Satoshi Kawata (ContributorSec. 2 Sec. 3)Springer 2015/06 174
  • 尾崎 幸洋 (Contributor２章、5.1章)講談社 2015/03 4061569023 288
  • 尾崎 幸洋; 勝本 之晶; 森田 成昭; 山本 茂樹; 森澤 勇介; 佐藤 春実 (Joint work)培風館 2015/01 4563046205 195

Conference Activities & Talks

  • Yusuke Morisawa; Yugo Higaki
    SPIE Nanoscience + Engineering, 2022  2022/08  San Diego, CA  SPIE
     
    We measured FUV spectra for a neat liquid of cyclohexane, methyl cyclohexane, tetrahydropyrane, methyl tetrahydropyrane and their hydroxyl derivatives by attenuated total reflection (ATR) technique, and assigned their transition using TD-DFT calculation. Moreover, we also investigated these spectra to discuss the changes in electronic states of sigma orbital of cyclohexane by introducing the oxygen substituted to the carbon and hydrogen atom.
  • 森澤 勇介; 上野 那美; 山﨑 渓太; 山口 礼央
    第82回分析化学討論会  2022/05  茨城大学  日本分析化学会
  • 佐々木 亮輔; 森澤 勇介
    第82回分析化学討論会  2022/05  茨城大学  日本分析化学会
     
    Y1107、ポスター賞受賞
  • 森澤 勇介; 檜垣 優悟
    日本化学会第102春季年会  2022/03 
    F302-3am-11
  • Changes in electronic states of solids of aliphatic alkane investigated by ATR Far-Ultraviolet spectroscopy  [Invited]
    Yusuke Morisawa
    Pacifichem 2021  2021/12 
    Far-ultraviolet (FUV) spectroscopy holds great potential in revealing changes in electronic states, especially for molecules in condensed phases regarding effect of intermolecular interactions. Since the molar absorption coefficient is very high (~105 mol-1 dm3 cm-1) in the FUV region, the electronic transitions mainly for molecules in the gas phase has been investigated for a long time. On the other hand, in terms of those in the condensed phase transmittance spectra could not measure because of high molecular density, and reflection spectroscopy has been used to observe spectra of solid samples in the FUV region. Accordingly, electronic spectroscopy for transitions from sigma orbital in condensed phase has been a relatively undeveloped research area. We have recently developed a totally new UV spectrometer based on attenuated total reflection (ATR) that enables us to measure spectra of liquid and solid samples in the 140–300 nm region. Liquid n- and branched alkanes were studied using ATR-FUV. FUV spectra of these molecules can be explained by quantum chemical calculation and almost similar to those in the gas phase. However, FUV spectra of solid alkanes show drastic alternations from those in the liquid phase. Changes in the orbital of alkanes in the solid phase were related to abnormal phase behavior of these molecules. We found differences in the FUV spectra between aliphatic alkanes with even and odd number of carbons in the solid phase. In this talk we will discuss detail.
  • Yusuke Morisawa
    Pacifichem 2021  2021/12 
    FUV spectroscopy in the 145-200 nm region has recently been a matter of intense interest because many kinds of materials in the condensed phase. Rapid progress of the studies has been introduced by the development of attenuated total reflection spectroscopy in the FUV region (ATR-FUV), which has enabled us to measure the spectra in the complete FUV region for liquid and solid samples without facing problems such as peak saturation. Moreover, significant progresses of quantum chemical calculations for electronic excitation states of molecules improve our interpretations of the FUV spectra. There are series of studies investigated the FUV region of various molecules by ATR-FUV spectroscopy; namely, water and aqueous solutions, amides in the liquid phase and alkanes in the solid phase. In the aqueous solution of alkali halides, charge-transfer-to-solvent bands of halide anions, I-, Br- and Cl- were observed in the region of 185-250, 175- 220, and 170-190 nm, respectively. Moreover, the effect of alkali cation (Li+, Na+, K+, Rb+ Cs+) on the first electronic transition of liquid water which is seen around 150 nm were studied by ATR-FUV spectroscopy. This effect was also investigated for other metal cations. These studies show the electronic states of solvents were changed by ions in the solution and the changes in electronic states were reflected in the electronic transition of the solvents. ATR–FUV spectra in the 145–260 nm range were observed for 5 liquid amides to investigate the intermolecular interactions based on their electronic transitions in the liquid phase. The peak wavelengths for the observed absorption bands in the 180–200 nm range and corresponding spectra measured in a gas phase by Kaya et al. were investigated. The gas-to-liquid shift of the band was different for different molecules. The blue shift was observed only for NdMF, and all other molecules yielded the red shift; it is particularly large for FA and NMF due to hydrogen bonding of NH---O=C.
  • Prospect of far ultraviolet spectroscopy in biomedical applications  [Not invited]
    Hidetoshi Sato; Kosuke Hashimoto; Bibin Andriana; Yusuke Morisawa; Yukihiro Ozaki
    Pacifichem 2021  2021/12 
    Far Ultraviolet (FUV) spectroscopy attracts keen interest of biological researchers. We apply FUV spectroscopy to study kinetics of the very surface of plasma membrane and its reaction with water in a live cell. FUV spectroscopy is able to give information of energy states σ electrons as well as π electrons. As any molecule has high absorption coefficient to the FUV light, a FUV spectrometer usually employs attenuated total reflection (ATR) method to obtain spectra of condensed matters. It is often applied with molecular orbital calculation techniques to study molecular structures and properties. In contrast, we have been interested in the optical property of the evanescent light at the surface of ATR prism in FUV spectroscopy. Since the wavelength is 120-200 nm, the ATR/FUV spectrometer collects information of the sample in a narrow space of less than 100 nm thickness from the ATR prism surface. Hence, it is able to observe the very surface of live cell exclusively. In the present basic study, we have obtained spectra of biological molecules such as DNA, sugar and proteins, and discuss the possibility and potential of the FUV applications in future.
  • Yusuke Morisawa; Nami Ueno; Mutsumi Imawari
    The 20th International conference on Near Infrared Spectroscopy  2021/10  Online  ICNIRS2021
     
    Section I: Spectroscopy Theory and Chemometrics
  • Yugo Higaki; Yusuke Morisawa
    2021年度日本分光学会年次講演会  2021/10 
    BIII-02
  • Ryosuke Sasaki; Yusuke Morisawa
    2021年度日本分光学会年次講演会  2021/10 
    PII-01
  • Yusuke Morisawa; Nami Ueno
    SciX2021  2021/09 
    Ultraviolet (UV) spectroscopy in the 145-200 nm region has recently been a matter of intense interest because many kinds of materials in the condensed phase. Rapid progress of the studies has been introduced by the development of attenuated total reflection spectroscopy in the FUV region (ATR-FUV), which has enabled us to measure the spectra in the complete Far-UV region for liquid and solid samples without facing problems such as peak saturation.1 Moreover, significant progresses of quantum chemical calculations for electronic excitation states of molecules improve our interpretations of the FUV spectra. There are series of studies investigated the FUV region of various molecules by ATR-FUV spectroscopy. In the aqueous solution of alkali halides, charge-transfer-to-solvent bands of halide anions, I-, Br- and Cl- were observed in the region of 185- 250, 175- 220, and 170-190 nm, respectively. Moreover, the effect of alkali cation (Li+, Na+, K+, Rb+ Cs+) on the first electronic transition of liquid water which is seen around 150 nm were studied by ATR-FUV spectroscopy. We also have studied the changes in electronic states of polyethylene glycol by coordination with Li+ in the highly concentrated solution. These studies show the electronic states of solvents were changed by ions in the solution and the changes in electronic states were reflected in the electronic transition of the solvents. In this presentation we will show results of ATR-FUV spectra of super-concentrated aqueous electrolytes (SAE) (>21 mol/kg), called hydrate melt (HM). These very concentrated aqueous solution have strong attention because Li-ion batteries used SAE as electrolyte have the high performance over 3.5V, although water is used as solvent. As a reason for a large potential window, We will have presented results of ATR-FUV spectra of SAE. We concluded that the band gap of water in SAE is very much enlarged by coordination with Li ion.
  • Ryosuke Sasaki; Mayu Kikuchi; Yusuke Morisawa
    日本分析化学会第70年会  2021/09 
    Y1006
  • Yugo Higaki; Yusuke Morisawa
    Annual Meeting of Japan Society for Molecular Science (2021）  2021/09 
    1C05
  • Yusuke Morisawa; Mutsumi Imawari; Nami Ueno
    11th International conference on advanced vibrational spectroscopy (ICAVS11)  2021/08  Online 
    Hydrate Melt (HM) is a high-concentration lithium salt aqueous solution composed of TFSI and BETI mixed anions. Since it promotes the coordination of lithium ions with strong Lewis acidity to water molecules, it is possible to improve the upper limit of the electromotive force of the water system to 3.0 V or more even though it is a water system electrolyte. It is well known that the molar ratio of HM is LiTFSI: LiBETI: H2O = 0.7: 0.3: 0.2. MD calculations predicted that water did not form a hydrogen bond network in HM. In this study, we investigated aqueous solutions with this unique hydrogen-bonding environment using near-infrared spectroscopy, which makes it easier to observe hydrogen-bond-free species which is difficult to observed in fundamentals. As a result, it was found that a sharp absorption band characteristic of HM was observed on the high frequency side of the peak of the saturated aqueous solution, which was not observed in the Raman spectrum. Aqueous solutions of single and mixed salts of LiTFSI, LiBETI and LiFTS were observed by FT-NIR. Fig. shows the Li (BETI) concentration dependence of the NIR spectrum ν1 + ν3 region of water in the Li (TFSI / BETI) mixed salt aqueous solutions. The solution with 5.0M Li+ means the nearly saturated aqueous solution of LiTFSI. Adding LiBETI, a higher concentration electrolyte aqueous solution can be prepared. From NIR spectra (a), there are two bands in 7100 and 6850 cm-1. The absorption of 6850 cm-1 is a band due to 2ν2 + ν3 of water, which is less affected by changes in the hydrogen bond environment.The second derivative spectra (b) revealed that by adding LiBETI, a new sharp peak appeared near 7200 cm-1. On the other hand, the peak of 7100 cm-1 becomes smaller with the concentration increases. The peak around 7200 cm-1 should assigned to component that is particularly large in the mixed salt, and it is considered that the water is coordinated with Li+ as a Lewis base.
  • Yusuke Morisawa; Nami Ueno
    SPIE Nanoscience + Engineering, 2021  2021/08  San Diego, CA  SPIE
     
    FUV spectroscopy in the 145-200 nm region has recently been a matter of intense interest because many kinds of materials in the condensed phase. Rapid progress of the studies has been introduced by the development of attenuated total reflection spectroscopy in the FUV region (ATR-FUV), which has enabled us to measure the spectra in the complete FUV region for liquid and solid samples without facing problems such as peak saturation. Moreover, significant progresses of quantum chemical calculations for electronic excitation states of molecules improve our interpretations of the FUV spectra. We will present an investigation about the FUV spectroscopy for aqueous solutions of highly concentrated alkali-metal salts, named hydrate-melt which can be used as high-performance electrolytes.
  • 減衰全反射遠紫外(ATR-FUV)分光法を用いたスクロースの電子状態研究
    佐々木 亮輔; 菊池 真由; 森澤 勇介
    第81回分析化学討論会  2021/05
  • Yusuke Morisawa
    The 4th Aquaphotomics International Conference  2021/03
  • 減衰全反射遠紫外分光分析法を用いた多環式アルカンの電子状態の研究  [Not invited]
    檜垣 優悟; 森澤 勇介
    日本化学会第101季年会  2021/03 
    A04-3am-02
  • Investigation for electronic transitions of cycloalkane observed in far ultraviolet region  [Not invited]
    森澤勇介; 檜垣優悟; 立花慎; 尾崎幸洋
    日本化学会第101春季年会  2021/03 
    [A04-3am-01]
  • 溶液中の分子間相互作用による近赤外吸収強度の増強・減衰効果の 研究  [Invited]
    森澤勇介
    第36回近赤外フォーラム  2020/11 
    NIR Advance Aawrd 受賞講演 I-05
  • 高濃度リチウム塩水溶液中の水の分光 研究  [Not invited]
    森澤勇介; 井廻睦美; 竹腰真聡; 上野那美
    2020年度 日本分光学会年次講演会  2020/10
  • Yusuke Morisawa
    SciX2020 
    MOLEC-OD5.1
  • 高濃度リチウム塩水溶液中の水の電子状態の研究  [Not invited]
    森澤勇介; 竹腰真聡; 上野那美
    日本分析化学会69年会  2020/09 
    H1006 （トピックと展望に選出）
  • 高濃度リチウム塩水溶液中の水の電子状態の研究  [Not invited]
    森澤 勇介; 竹腰 真聡; Zaitceva Anna
    日本化学会第100春季年会  2020/03
  • Application of ATR - FUV spectroscopy for the analysis of the coordinate structure in concentrated solutions about alkali metal complexes  [Not invited]
    UENO, Nami; SATO, Harumi; WAKABAYASHI, Tomonari; MORISAWA, Yusuke
    日本化学会第100春季年会  2020/03
  • Yusuke Morisawa
    SciX2019  2019/10  Palm Spring,CA  FACSS
     
    19SPSJ02: VUV/FUV/DUV II (179)
  • 遠紫外分光法を用いたシクロヘキサンおよびそのメチル化体の電子状態の研究  [Not invited]
    森澤 勇介; 檜垣 優悟
    分子科学討論会2019  2019/09 
    4P025
  • 高濃度電解質溶液における溶媒の電子状態に対するイオンの影響  [Not invited]
    上野 那美; 若林 知成; 佐藤 春実; 森澤 勇介
    分子科学討論会2019  2019/09 
    3C12
  • Investigation for sigma orbitals in normal- and cyclo-alkanes using ATR-FUV  [Invited]
    Yusuke Morisawa
    SPIE Nanoscience + Engineering, 2019  2019/08  San Diego, CA  SPIE
     
    Paper 11086-22
  • 減衰全反射遠紫外分光法と振動分光法を用いたLi塩を含むDeep Eutectic Solventsのイオン形態の分析  [Not invited]
    西木戸 和貴; 森澤 勇介
    第78回分析化学討論会  2019/05 
    Y1005
  • 低周波数振動分光法を用いた生分解性ポリマーの光学活性添加物による結晶化抑制・促進効果の分析  [Not invited]
    森澤 勇介; 池田 有理; 濱田 望央; 佐藤 春実
    第78回分析化学討論会  2019/05 
    C1001
  • シクロアルカンの遠紫外分光研究  [Not invited]
    森澤勇介; 檜垣優悟; 立花慎; 尾崎幸洋
    2019年度日本分光学会年次講演会  2019/05
  • アルカリ金属錯体の電子状態の理論的 解釈  [Not invited]
    上野那美; 若林知成; 森澤勇介
    2019年度日本分光学会年次講演会  2019/05
  • Study of Electronic States of Deep Eutectic Solvents by using Attenuated Total Reflectance Spectroscopy in the Far-UV spectroscopy  [Not invited]
    Kazutaka Nishikido; Yusuke Morisawa
    Japan-Taiwan Medical Spectroscopy International Symposium  2016/12
  • Study of electronic transitions of polymers by using attenuated total reflectance spectroscopy in the far-UV region  [Not invited]
    Yusuke Morisawa; Erika Tanimura; Yukihiro Ozaki
    Japan-Taiwan Medical Spectroscopy International Symposium  2016/12
  • Decreasing of electronic transitions of Poly Ethylene Glycol Applied to Li/PEG complex  [Not invited]
    Nami Ueno; Yusuke Morisawa
    Japan-Taiwan Medical Spectroscopy International Symposium  2016/12
  • Electronic state of nano carbon and nano carbon/polymer nanocomposite studied by attenuated total reflectance (ATR) far- and deep-ultraviolet spectroscopy  [Not invited]
    Kenta Kobashi; Yusuke Morisawa; Harumi Sato; Ichiro Tanabe; Takeyoshi Goto; Yukihiro Ozaki
    Japan-Taiwan Medical Spectroscopy International Symposium  2016/11
  • Study of Electronic States of Molecules in the Condensed Phase by Using Attenuated Total Reflectance Far-UV Spectroscopy  [Not invited]
    Yusuke Morisawa
    SCIX 2016  2016/09
  • Electronic States of Composite Polymer Electrolyte Composed of PEG and Lithium-salts.  [Not invited]
    Nami Ueno; Tomonari Wakabayashi; Yusuke Morisawa
    SCIX 2016  2016/09
  • 遠紫外分光と量子化学計算によるイミダゾリウム系イオン液体の電状態研究  [Not invited]
    田邉 一郎; 藏脇 悠司; 森澤 勇介; 尾崎 幸洋
    第10回分子科学討論会2016神戸  2016/09
  • ナノカーボン材料およびポリマーナノコンポジットの電子状態の研究  [Not invited]
    小橋 健太; 田邉 一郎; 森澤 勇介; 佐藤 春実; 後藤 剛喜; 尾崎 幸洋
    第10回分子科学討論会2016神戸  2016/09
  • 減衰全反射遠紫外分光法による凝縮相中の分子間相互作用による電子状態の変化  [Not invited]
    Yusuke Morisawa
    第10回分子科学討論会2016神戸  2016/09
  • ネオンマトリックス中に捕捉されたビスマス二量体のPLマップにおけるサテライト構造  [Not invited]
    遠藤 あすか; 畑中 美穂; 森澤 勇介; 若林 知成
    第10回分子科学討論会2016神戸  2016/09
  • ポリエチレングリコール酸素原子へのカチオン配位による電子状態の変化  [Not invited]
    野 那美; 森澤 勇介; 若林 知成
    第10回分子科学討論会2016神戸  2016/09
  • Study of electronic transitions by using attenuated total reflectance spectroscopy in the far-UV region  [Not invited]
    Yusuke Morisawa; Shin Tachibana; Masahiro Ehara; Yukihiro Ozaki
    SPIE Nanoscience + Engineering 2016  2016/08
  • 減衰全反射遠紫外スペクトルを用いたイオン液体中のアニオンについての電子 状態の研究  [Not invited]
    森澤勇介; 田邉一郎
    平成28年度 日本分光学会年次講演会  2016/05
  • ポリアルカングリコールの分子構造による電子状態の変化  [Not invited]
    上野那実; 森澤勇介
    平成28年度 日本分光学会年次講演会  2016/05
  • 遠紫外分光法と量子化学計算を利用したイオン液体の電子状態研究  [Not invited]
    田邉一郎; 藏脇悠司; 森澤勇介; 尾崎幸洋
    平成28年度 日本分光学会年次講演会  2016/05
  • 減衰全反射型遠紫外〜深紫外分光法によるナノカーボン材料およびポリマーナノ コンポジットの電子状態の研究  [Not invited]
    小橋健太; 田邉一郎; 森澤勇介; 佐藤春実; 後藤剛喜; 尾崎幸洋
    平成28年度 日本分光学会年次講演会  2016/05
  • ATR-FUV 分光法による CTTS バンドの観察：塩化ナトリウムの分光学的定量法  [Not invited]
    池羽田晶文; 森澤勇介
    平成28年度 日本分光学会年次講演会  2016/05
  • ポリアルカングリコールの遠紫外スペクトルの帰属と電子状態 の固液変化についての研究  [Not invited]
    上野那美; 森澤勇介
    日本化学会 第96春季年会 (2016)  2016/03
  • 減衰全反射型遠紫外～深紫外分光法によるナノカーボン材料お よびナノカーボン/ポリマーナノコンポジットの電子状態評価  [Not invited]
    小橋健太; 田邉一郎; 森澤勇介; 佐藤春実; 後藤剛喜; 尾崎幸洋
    日本化学会 第96春季年会 (2016)  2016/03
  • 減衰全反射遠紫外分光法による単結合からなるイオン液体の電 子状態の研究  [Not invited]
    森澤勇介; 曽我賢冶; 田邉一郎
    日本化学会 第96春季年会 (2016)  2016/03
  • 減衰全反射遠紫外分光と量子化学計算によるイミダゾリウム系 イオン液体の電子状態研究  [Not invited]
    Ichiro Tanabe; Yuji Kurawaki; Yusuke Morisawa; Yukihiro Ozaki
    日本化学会 第96春季年会 (2016)  2016/03
  • 電解酸化により発生・蓄積させたチイレニウムイオンの反応性  [Not invited]
    堀内 俊; 林 竜太朗; 清水章弘; 松本浩一; 宮本侑; 森澤勇介; 若林知成; 吉田潤一
    日本化学会 第96春季年会 (2016)  2016/03
  • Yusuke Morisawa
    日本分光学会遠紫外分光部会 第1回講演会  2016/01  関西学院大学梅田キャンパス  日本分光学会遠紫外分光部会
  • Study of electronic states of aqueous solutions of sodium halides by using temperature dependence attenuated total reflectance spectroscopy in the far ultraviolet region  [Not invited]
    Yuka Nishikawa; Yusuke Morisawa; Akifumi Ikehata
    Pacifichem 2015  2015/12
  • Study of electronic state of polyethylene glycol using attenuated total reflectant spectrosopy in far ultraviolet  [Not invited]
    Nami Ueno; Yusuke Morisawa
    Pacifichem 2015  2015/12
  • Study of surface analysis of polystyrene nano particle by using attenuated total reflectance spectroscopy in the far-UV region  [Not invited]
    Yusuke Morisawa
    Pacifichem 2015  2015/12
  • Study of absorption intendsities in the near infrared region for the first and second overtones of OH and NH stretching vibration with hydrogen bonding  [Not invited]
    Misaki Tatsumi; Yusuke Morisawa
    Pacifichem 2015  2015/12
  • Far UV absorption spectroscopy of linear polyyne molecules in solutions  [Not invited]
    Yoriko Wada; Usuke Morisawa; Tomonari Wakabayashi; Yukihiro Ozaki
    Pacifichem 2015  2015/12
  • Investigation of Electronic States of Nano Carbon/Polymer Nanocomposites by Attenuated Total Reflectance-Ultraviolet Spectroscopy  [Not invited]
    Kenta Kobashi; Ichiro Tanabe; Yusuke Morisawa; Harumi Sato; Takeyoshi Goto; Yukihiro Ozaki
    Scix 2015  2015/09 
    (110)
  • Studies of Electronic States of CNT/Rubber Nanocomposites by using Attenuated Total Reflectance Spectroscopy in the Ultraviolet Region  [Not invited]
    Yusuke Morisawa; Kenta Kobashi; Ichiro Tanabe; Harumi Sato; Takeyoshi Goto; Yukihiro Ozaki
    Scix 2015  2015/09 
    (109)
  • Temperature Dependence of FUV Spectra for Aqueous Solutions of Alkali Halide to the Freezing-point of Eutectic  [Not invited]
    Yusuke Morisawa; Yuka Nishikawa; Akifumi, Ikehata
    Scix 2015  2015/09 
    (97)
  • 減衰全反射紫外分光法によるカーボン材料/ポリマーナノコンポジットの電子状態の研究  [Not invited]
    小橋 健太; 田邉 一郎; 森澤 勇介; 佐藤 春実; 後藤 剛喜; 尾崎 幸洋
    第9回 分子科学討論会  2015/09 
    4P051
  • Nami Ueno; Yusuke Morisawa
    第9回 分子科学討論会  2015/09 
    4P049
  • 森澤勇介; 立花 慎; 池羽田 晶文; 江原 正博; 尾崎 幸洋
    第9回 分子科学討論会  2015/09 
    4D07
  • 遠紫外分光法によるナトリウムハロゲン化物水溶液中のハロゲン化物イオンCTTSバンドに現れる変化からみた,低温溶液および固体中の電解質水和状態に関する研究  [Not invited]
    西川由華; 森澤勇介
    日本分析化学会年会  2015/09 
    J3005
  • 第一,第二,第三級アルコールのOH伸縮振動第一,第二倍音の水素結合の有無による吸収強度の変化の研究  [Not invited]
    立美美沙紀; 森澤勇介
    日本分析化学会年会講演要旨集  2015/09 
    J3002Y
  • 減衰全反射遠紫外分光法によるポリエチレングリコールの表面分析  [Not invited]
    森澤勇介; 上野那美
    日本分析化学会年会  2015/09 
    J3007
  • 遠紫外CTTSバンドを用いた塩化物イオンの定量  [Not invited]
    池羽田晶文; 森澤勇介
    日本分析化学会年会  2015/09 
    P1128
  • Effect of Intermolecular Interactions on Absorption Intensities of the First and Second Overtones of OH and NH Stretching Vibrations Studied by Near-Infrared Spectroscopy  [Not invited]
    Yusuke Morisawa; Misaki Tatsumi; Yukihiro Ozaki
    8th International Conference on Advanced Vibrational Spectroscopy  2015/08 
    In the present study we have investigated effects of intermolecular interactions on absorption intensities of the OH and NH the first and second overtones of 1-octanol, and pyrrole in none polar solvent by using NIR spectroscopy. We selected these molecules because they easily form hydrogen-bonding aggregates while in enough dilute solutions they do not form hydrogen-bonding species and have an intermolecular interaction with a solvent (solvent effect). We investigated higher order overtones than previous work.
  • 池羽田 晶文; 西川 由華; 森澤 勇介
    日本分析化学会第75回分析化学討論会  2015/05  山梨大学甲府キャンパス  日本分析化学会
     
    D2012 （講演者 池羽田）
  • 森澤 勇介; 越智 高志
    日本分析化学会第75回分析化学討論会  2015/05  山梨大学甲府キャンパス  日本分析化学会
     
    D2011
  • 上野 那美; 森澤 勇介
    日本化学会第95春季年会  2015/03  日本大学理工学部 船橋キャンパス  日本化学会
     
    3H3-39 (講演者 上野）
  • 立美 美沙紀; 寺本幸紘; 森澤 勇介
    第 30 回記念近赤外フォーラム  2014/11  筑波大学総合交流会館 
    JCNIRS Student Travel Award受賞 （講演者 立美）
  • Yusuke Morisawa; Erika Tanimura; Shin Tachibana; Masahiro Ehara; Yukihiro Ozaki
    morisawayusuke  2014/10  Grand Sierra Resort, Reno, Nevada  FACSS
     
    Far-ultraviolet (FUV) spectroscopy has been a subject of considerable interest because it provides unique information about the electronic states and their transitions of molecules which usual UV region cannot provide. However, investigations on FUV spectra in the condensed phase have long been rare because of the difficulty in observing whole FUV bands of liquid and solid samples owing to their strong absorption. Thus, studies of FUV spectra in the condensed phase give the novel information of the energy gap of the frontier orbital and will use in the precise consideration of chemical reaction in the condensed phase. Recently, we developed an attenuated total reflection (ATR) technique for use in the FUV region. By using the ATR-FUV, we can measured FUV spectra more feasibly. In this presentation, ATR-FUV spectra were measured for low-density polyethylene (LDPE) films prepared by two different methods. A pressed LDPE film showed the similar spectrum to liquid n-alkane, while the spectrum of a cast LDPE film was totally different feature from the press film. The 8.0-eV band was weaken, and two bands peaked at 6.3 and 5.5 eV were appeared. The component which have the novel 3-bands component could be found on the nano-surface because the penetration depth of the ATR-FUV is lower than 100 nm, and the transmittance spectrum of cast LDPE film doesn`t show thecomponent. At the lower energy region very small signal was found at 4.5eV. Those features are similar to low-temperature solid of n-alkane. The origin of these spectral changes was investigated by quantum chemical calculations that calculate orbital energy and electronic transitions of model dimer by changing the intermolecular distance between two molecules. These results provide new insight: valence molecular orbitals, even σ orbitals, interact with their neighbors in the condensed phase. As a result, the band gap energy is reduced by about 3 eV, which corresponds to one third of the liquid state. The surface of the cast LDPE film shows the reduction on the surface of casting film at room temperature.
  • 森澤 勇介; 谷村 恵里香; 江原 正博; 尾崎 幸洋
    morisawayusuke  2014/09  広島大学  日本分析化学会
     
    I3009
  • 後藤剛喜; 東昇; 立花慎; 森澤勇介; 尾崎幸洋
    ケミカルエンジニヤリング  2014/03
  • タイトル(英語)  [Not invited]
    講演者
    会議名(英語)  2014/03  開催地(英語)  主催者(英語)
     
    概要(英語)
  • タイトル(英語)  [Not invited]
    講演者
    morisawayusuke  2014/03
  • 石川大太郎; 森澤 勇介; 尾崎幸洋; 保科宏道; 佐藤周作; 入澤昭好; 今村元規
    テラヘルツ分光法の最先端 Ⅶ  2013/10  京都大学  テラヘルツ分光法の最先端 Ⅶ
     
    ポスター P-22
  • 森澤 勇介; 寺本幸紘; 尾崎幸洋
    SCIX 2013  2013/10  Milwaukee, WI  SCIX 2013
     
    Poster；FUV Spectrum of methanol in the pure-liquid states have already reported by using attenuated total reflection (ATR) - FUV spectroscopy. Concentration dependence of tail structure in the region of 190-210 nm has been observed. The molar absorption coefficient of the tail structure was decreasing with the increase of the concentration of methanol. In the present study, temperature dependence of the tail structure for the alcohol-hexane solution of the different concentration. Temperature dependence of the molar absorption coefficients were increasing with the increasing of temperature for the conc-solution, on the other hand, that for the diluted solution were decreasing. We will discuss about this alternation of the temperature dependence
  • 植松祐樹; 森澤 勇介; 尾崎幸洋; 江原正博
    SCIX 2013  2013/10  Milwaukee, WI  SCIX 2013
     
    Poster；Benzene and its derivatives are basic chemical compounds. In the present study, the FUV spectra of benzene and its derivatives in liquid phase are examined by an attenuated total reflection far-ultraviolet spectrophotometer (ATR-FUV) which was recently developed by our research group. [2] Different concentration solutions (1.0 M ~ neat) of benzene and eight mono-substituted benzenes (toluene, chlorobenzene, bromobenzene, anisole, benzyl alcohol, acetophenone, nitrobenzene, aniline) were prepared in cyclohexane. The ATR-FUV spectra of the sample solutions were measured in the wavelength from 145 to 300 nm. To examine how the inter-molecular interaction among benzene units affects the S0→S3 transition, the electronic spectra of chlorobenzene molecules for monomer, dimer and trimer with ππ stacking configuration were calculated by quantum chemical calculations with a time-dependent density functional theory (TD-DFT) method.
  • 森澤 勇介; 大西絵里香; Kummetha Reddy; 石川大太郎; 尾崎幸洋; 佐藤春実; 石井伸弥; 鈴木陽; 保科宏道
    SCIX 2013  2013/10  Milwaukee, WI  SCIX 2013
     
    Oral；Low-frequency Raman and Terahertz spectroscopies provide information about intermolecular vibrations such as hydrogen-bonds, which reflect the conformational changes in polymers. Nylon is one of the most widely used synthetic fibers, and its phase behavior and crystal structures have extensively been studied by various methods. The neighboring molecular chains of Nylon are connected by strong hydrogen bonds (N-H…O=C), which dominate the physical behaviors of Nylon. In this study, we have studied temperature-dependent structural changes of Nylon 6 by using low-frequency Raman, Terahertz spectroscopies and quantum chemical calculations of the spectra.
  • 後藤剛喜; 森澤 勇介; 尾崎幸洋; 池羽田晶文
    UV-DUV Plasmonics and Nanophotonics Workshop (UPN2013)  2013/10  Osaka  UV-DUV Plasmonics and Nanophotonics Workshop (UPN2013)
     
    We report the first electronic transition of vicinal water of an α-alumina surface probed by variable-angle attenuated total reflection far-ultraviolet (VA-ATR-FUV) spectroscopy. As the path length of the probe light (de) is shorter from 94.4 to 36.5 nm, (1) the band is blue-shifted by 1 nm and (2) the absorption coefficient increases by 1.9 - 104 cm-1. The measured VA spectra were linearly decomposed into the spectra of bulk and interfacial water based on the dependence of the spectral changes on the de values. The bands of the bulk and interfacial water appear at 147.8 and 143.4 nm. The band shapes of liquid water show their own hydrogen bond (H-bond) structures. Specifically, the band shapes of bulk and interfacial water are very close to those of amorphous and hexagonal crystal ice of water, respectively.
  • 若林 知成; 森澤 勇介; 柴田 宙延; 女木; 健司; 瀧; 智司; 和田 資子
    第7回分子科学討論会  2013/09  京都テルサ  第7回分子科学討論会
     
    2C03
  • 植松祐貴; 森澤 勇介; 尾崎幸洋; 江原正博
    第7回分子科学討論会  2013/09  京都テルサ  第7回分子科学討論会
     
    2D07
  • 森澤 勇介; 立花慎; 谷村恵里香; 江原正博
    第7回分子科学討論会  2013/09  京都テルサ  第7回分子科学討論会
     
    4C16
  • 大西絵里香; 森澤 勇介; Kummetha Raghunatha Reddy; 石川大太郎; 尾崎幸洋; 佐藤春実; 山本茂樹; 保科宏道
    第62回高分子討論会  2013/09  金沢  第62回高分子討論会
     
    1Pe047 ポスター発表（大西）
  • 森澤 勇介; 江原正博; 尾崎幸洋
    日本分析化学会第62年会  2013/09  近畿大学  日本分析化学会第62年会
     
    K1010 依頼公演（口頭 森澤）
  • 森澤 勇介; 寺西拓也
    日本分析化学会第62年会  2013/09  近畿大学  日本分析化学会第62年会
     
    P3012（ポスター 森澤）
  • 後藤剛喜; 森澤 勇介; 尾崎幸洋; 池羽田晶文
    日本分析化学会第62年会  2013/09  近畿大学  日本分析化学会第62年会
     
    K1010 口頭発表（後藤）
  • 後藤剛喜; 森澤 勇介; 尾崎幸洋; 東昇; 池羽田晶文
    日本分析化学会第62年会  2013/09  近畿大学  日本分析化学会第62年会
     
    P3015（ポスター 後藤）
  • 谷村恵里香; 森澤 勇介; 尾崎幸洋; 佐藤春実; 苅山直美 東
    日本分析化学会第62年会  2013/09  近畿大学  日本分析化学会第62年会
     
    Y1017（ポスター 谷村） ポスター賞受賞
  • 立花慎; 森澤 勇介; 苅山直美; 後藤剛喜; 尾崎
    日本分析化学会第62年会  2013/09  近畿大学  日本分析化学会第62年会
     
    K1015 （口頭 立花）
  • 大西絵里香; 森澤 勇介; Kummetha Raghunatha Reddy; 石川大太郎; 尾崎幸洋; 山本茂樹; 佐藤春実; 保科宏道
    日本分析化学会第62年会  2013/09  近畿大学  日本分析化学会第62年会
     
    K1014 （口頭 大西）
  • 鈴木利明; 森澤 勇介; 南聡史; 尾崎幸洋; 久津間保徳; 芦田晃嗣; 金子忠昭; 伊藤民武; 三浦健
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    A-041 口頭発表 （鈴木利明）
  • 島田和明; 松本 浩一; 森澤 勇介; 若林 知成; 柏村 成史; 菅誠治; 吉田潤一
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    P-136（島田）
  • 保科宏道; 森澤 勇介; 石井伸也; 鈴木晴; 大谷知行; 山本茂樹; 佐藤春実; 尾崎幸洋
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    C-001 口頭発表 （保科宏道）
  • 大西絵里香; 森澤 勇介; 石川大太郎; 佐藤春実; 山本茂樹; 石井伸也; 鈴木晴; 保科宏道
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    P137 ポスター発表 （大西絵里香）
  • 後藤剛喜; 森澤 勇介; 尾崎幸洋; 池羽田晶文
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    P316ポスター発表 （後藤剛喜）
  • 真田和俊; 森澤 勇介; 野村聡史; 尾崎幸洋
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    P262ポスター発表 （真田和俊）
  • 森澤 勇介; 末永 勇作; 佐藤春実; 保科宏道; 尾崎幸洋
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    C-001 ポスター発表 （森澤勇介）
  • 和田資子; 若林 知成; 森澤 勇介
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    P-208 （和田資子）
  • 森澤 勇介; 菅亜里沙; 尾; 寺本幸紘
    7th International Conference on Advanced Vibrational Spectroscopy  2013/08  Kobe  7th International Conference on Advanced Vibrational Spectroscopy
     
    A-056 口頭発表 （森澤）
  • 谷村 恵里香; 森澤 勇介; 尾崎 幸洋; 佐藤 春美; 苅山 直美; 東
    第59回高分子研究発表会  2013/07  兵庫県民会館（神戸）  第59回高分子研究発表会
     
    Pb-44
  • 植松 祐貴; 森澤 勇介; 泰永 愛佳; 尾崎
    33rd International Conference on Solution Chemistry  2013/07  Kyoto Terrsa, Kyoto, Japan  33rd International Conference on Solution Chemistry
     
    2PB06
  • 森澤 勇介; 泰永 愛佳; 福田 良一; 江原
    33rd International Conference on Solution Chemistry  2013/07  Kyoto Terrsa, Kyoto, Japan  33rd International Conference on Solution Chemistry
     
    3PB20
  • 大西絵理香; 森澤 勇介; K. R. Reddy; 石川大太郎; 尾崎幸洋; 佐藤春実; 山本茂樹; 石井伸也; 鈴木晴; 保科宏道
    19th European Symposium on Polymer Spectroscopy (ESOPS19)  2013/07  PRAGUE, CZECH REPUBLIC  19th European Symposium on Polymer Spectroscopy (ESOPS19)
     
    P-26 （ポスター賞受賞）
  • 山本茂樹; 森澤 勇介; 佐藤春実; 保科宏道; 尾崎幸洋
    19th European Symposium on Polymer Spectroscopy (ESOPS19)  2013/07  PRAGUE, CZECH REPUBLIC  19th European Symposium on Polymer Spectroscopy (ESOPS19)
     
    P-05
  • 池羽田 晶文; 森澤 勇介; 後藤剛喜; 東昇; 尾崎幸洋
    第73回分析化学討論会  2013/05  北海道大学函館キャンパス  第73回分析化学討論会
     
    波長200nm以下の遠紫外（FUV）領域に観測される溶媒の吸収はσ軌道やπ軌道といった外殻電子の遷移に起因する。これらは水素結合等の相互作用によって変化を受けやすい。本研究ではATR-FUV分光帆を用い、水素結合性分子であるメタノール（MeOH)を極性の異なる有機溶媒で希釈した際のFUVスペクトルを観測した。得られたスペクトルをmultivariate curve resolution （MCR)によって水素結合種に分解し、会合モデルによって会合分子数を推定した。
  • 谷村 恵里香; 森澤 勇介; 尾崎幸洋; 佐藤 春美; 苅山 直美; 東
    第73回分析化学討論会  2013/05  北海道大学函館キャンパス  第73回分析化学討論会
     
    Y1007
  • 森澤 勇介; 泰永 愛佳; 尾崎; 洋; 江原 正博
    第73回分析化学討論会  2013/05  北海道大学函館キャンパス  第73回分析化学討論会
     
    F1011 遠紫外領域に観測される許容電子遷移は大きな吸光係数を持つため、微小な領域（ナノメートル程度）の分子の電子状態を観測することができ、このような領域の組成や化学反応性を分析する手段として期待される。高分子の表面から数10ナノメートルはその表面物性を決定する重要な領域である。今回は化学構造の異なるナイロンを測定し、液体アミドとナイロンのスペクトルの比較及びナイロンの構造の違いによるスペクトルの結果を報告する。
  • 大西 絵里香; 森澤 勇介; 石川 大太郎; Kummetha Raghunatha Reddy; 尾崎幸洋; 佐藤 春美; 石井 伸弥; 木; 晴; 保科 宏道
    第73回分析化学討論会  2013/05  北海道大学函館キャンパス  第73回分析化学討論会
     
    Y1006
  • Spectroscopy  [Invited]
    Yusuke Morisawa; Daitarou Ishikawa; Shigeki Yamamoto; Toshiaki Suzuki; Yasutaka Kitahama; Yukihiro Ozaki
    光学  2013/04
  • 森澤 勇介; 後藤剛嬉; 池; 田晶文; 東昇; 尾崎幸洋
    Encyclopedia of Analytical Chemistry  2013/03 
    DOI: 10.1002/9780470027318.a9287
  • 森澤 勇介
    第28回近赤外フォーラム  2013/03  沖縄県男女共同参画センター てぃるる（沖縄県那覇市）  第28回近赤外フォーラム
  • 森澤 勇介; 菅亜里沙; 尾崎幸洋
    第28回近赤外フォーラム  2013/03  沖縄県男女共同参画センター てぃるる（沖縄県那覇市）  第28回近赤外フォーラム
  • 森澤 勇介; 中山篤史; 谷村恵里香; 佐藤春実; 苅山直美 東
    日本化学会第９３春季年会  2013/03  立命館大学びわこ・くさつキャンパス  日本化学会第９３春季年会
     
    減衰全反射（ATR)法を用いれば測定物と内部反射部材甲面からおよそ 波長の半分の分子の分光情報を観測することができる。遠紫外領域（140-200nm） ではその観測領域は数十ナノメートルとなる。これを高分子の表面分析に用いれば、 その接着性等の表面機能・物性の分析に力を発揮すると考えた。本研究ではポリ エチレンと側鎖に極性基を持った接着性樹脂の共重合体を遠紫外領域における 透過スペクトルとATRスペクトルを測定し、比較することでその表面構造の研究 を行ったので報告する。
  • 森澤 勇介; 泰永愛佳; 尾; 江原正博
    日本化学会第９３春季年会  2013/03  立命館大学びわこ・くさつキャンパス  日本化学会第９３春季年会
     
    当研究室独自で開発した減衰全反射遠紫外分光器を用いて、構造の異なる ５種類のナイロンの観測を行った。すると、ナイロンのスペクトルは液体アミド同様 のスペクトルが観測された。また、ナイロンの構造の違いがスペクトルに現れること がわかった。当日は、ナイロンのスペクトルと液体モノマーのスペクトルの比較およ び、量子化学計算による比較を行い議論する予定である。
  • 植松裕貴; 森澤 勇介; 尾崎幸洋; 泰永愛
    日本化学会第９３春季年会  2013/03  立命館大学びわこ・くさつキャンパス  日本化学会第９３春季年会
     
    ベンゼンとその誘導体は、遠紫外領域において強い吸光係数をもつため、これまでは気体状態における遠紫外スペクトルしか測定されていなかった。しかし、当研究室で開発された減衰全反射法を用いた遠紫外分光システム(ATR-FUV)により、液体状態におけるそれらの遠紫外スペクトルを簡便に測定できるようになった。本研究では、ベンゼンと7種類の一置換ベンゼンについて、それらの純液体および希釈溶液の遠紫外スペクトルの測定を行った。
  • 和田 資子; 若林 知成; 森澤 勇介
    日本化学会第９３春季年会  2013/03  立命館大学びわこ・くさつキャンパス  日本化学会第９３春季年会
  • 森澤 勇介
    日本分光学会関西支部  2013/03  近畿大学理工学部東大阪キャンパス  日本分光学会関西支部
     
    遠紫外光の減衰全反射法を用いれば内部反射部材から数十ナノメートル程度しみだした 光と試料の相互作用を観測することができ、吸収係数が大きく微小部の分光分析に適した この領域の特徴を最大限に生かすことができる。応用分析に必須となる凝縮相における遠 紫外スペクトルの遷移帰属について、基礎的な分子から高分子まで実験および理論的な研 究について紹介する。
  • 大西絵里香; 森澤 勇介; 石川大太郎; 山本茂樹; 尾崎幸洋; 佐藤春実; 石井伸也; 鈴木陽; 保科宏道
    The 9th SPSJ International Polymer Conference  2012/12  Kobe  The 9th SPSJ International Polymer Conference
     
    13P1G2-142b ポスター発表
  • 谷村恵里香; 森澤 勇介; 尾崎幸洋; 佐藤春実; 苅山直美 東
    The 9th SPSJ International Polymer Conference  2012/12  Kobe  The 9th SPSJ International Polymer Conference
     
    13P1G2-074b ポスター発表
  • 泰永愛佳; 森澤 勇介; 尾崎幸洋; 佐藤春実; 福田良一; 池羽田晶文; 東昇
    The 9th SPSJ International Polymer Conference  2012/12  Kobe  The 9th SPSJ International Polymer Conference
     
    13P1G2-073a ポスター発表
  • 後藤剛喜; 森澤 勇介; 池羽田晶文; 東昇; 尾崎幸洋
    日本分光学会年次講演会  2012/11  東京工業大学百年記念会館  日本分光学会年次講演会
     
    ポスター発表 P１４
  • 森澤 勇介; 谷村恵里香; 佐藤春実; 苅山直美
    日本分光学会年次講演会  2012/11  東京工業大学百年記念会館  日本分光学会年次講演会
     
    高分子表面の分析技術はその改質や修飾技術の発展とともに、重要な技術となってきた。 中でも、表面の分光学的情報は表面における分子レベル、官能基レベルといったミクロな視点での情報を与える。これまで減衰全反射(Attenuated Total Reflection、ATR)赤外(IR)分光法が官能基レベルでの表面の構造情報を与える分析手法としてよく用いられてきたが、その分析深さ（光のもぐりこみ深さ）はμm オーダーに達してしまう。ATR-FUV 領では分子の許容電子遷移に相当する強い吸収が観測され、nm サイズの領域からスペクトルを得ることができる。我々はこれまでにFUV 領域でのATR 法（ATR-FUV）分光法を開発してきた。ATR-FUV では分析深さ数十nmのATRスペクトルを観測することができる。高分子でATR-FUV を測定することができれば、高分子の数十nm に限定した表面の電子状態を観測することが可能である。
  • 保科宏道; 森澤 勇介; 大谷知行; 石井伸弥; 佐藤春実; 山本茂樹; 尾崎幸洋; 野田勇夫
    FACSS presents SciX 2012  2012/10  Kansas City, MO  FACSS presents SciX 2012
     
    oral presentation (370)
  • 山本茂樹; 森澤 勇介; 佐藤春実; 保科宏道; 石井伸弥
    FACSS presents SciX 2012  2012/10  Kansas City, MO  FACSS presents SciX 2012
     
    presentation (611)
  • 森澤 勇介; 池羽田晶文; 東昇; 尾崎幸洋
    FACSS presents SciX 2012  2012/10  Kansas City, MO  FACSS presents SciX 2012
     
    Oral Presentation (671）
  • 谷村恵里香; 森澤 勇介; 佐藤春実; 苅山直美 東
    FACSS presents SciX 2012  2012/10  Kansas City, MO  FACSS presents SciX 2012
     
    poster presentation (221)
  • 泰永愛佳; 森澤 勇介; 佐藤春実; 江原正博; 池羽田晶文; 東昇
    第6回分子科学討論会  2012/09  東京大学 本郷キャンパス  第6回分子科学討論会
     
    発表番号1C02；遠紫外領域（FUV：120-200 nm）におけるアミドの電子状態に関する研究は、これまでには実験的困難から気相や希薄溶液に限られていた。当研究室独自で開発した減衰全反射遠紫外（ATR-FUV）分光システム1)2)を用いることで、吸収強度の高い遷移を純溶液に対しても吸収飽和することなくピークとして測定することができる。さらに、サンプルへの潜り込み深さが数十nmであることを考慮に入れると固体の極表面測定への適用が期待される。以前に液体アミドの電子遷移の観測を行い、量子化学計算を用いて帰属を行った。液体アミドの中でも、 N-メチルアセトアミド（NMA）はナイロンのユニットモデルとして、その水素結合の構造の研究が他の分光法でも盛んに行われている。本研究では構造の異なるナイロンのATR-FUVスペクトルの観測を行い、200 nm付近には液体アミド同様の吸収が観測された。液体アミドとナイロンのスペクトルの比較およびナイロンの構造の違いによるスペ
  • 森澤 勇介; 立花慎; 泰永愛佳; 尾崎幸洋; 江原正博; 池羽田晶文; 東昇
    第6回分子科学討論会  2012/09  東京大学 本郷キャンパス  第6回分子科学討論会
     
    発表番号1D01;遠紫外(FUV)領域には分子のRydberg状態への遷移が存在し、これまで気相の分子の電子状態を対象にした研究が盛んに行われてきた。しかし、これらの遷移の多くは許容電子遷移であり、モル吸光係数が大きく、またほとんどの溶媒が吸収をもつために、凝縮相に対しては透過法では測定が困難であった。従って、FUV領域の遷移、特にRydberg状態への遷移が凝集相においてどのような影響を受けるかということはほとんどわかっていない。我々は、減衰全反射(ATR)法を用いたFUV分光器を開発した。サンプル交換が容易で吸収飽和しないATR-FUV分光器を用いることで、容易に液体のFUV領域の吸収スペクトルの観測ができる[1]。これまでに、アルコール[2]、アルカン[3]、ケトン[4]、等の有機液体を系統的に測定した。化学構造の違いに対する吸収ピーク波長および吸収強度の変化を検証し、気相スペクトルとの比較や、量子化学計算で求まる電子励起エネルギーとの比較などの帰属法を検討
  • 山本茂樹; 森澤 勇介; 佐藤春実; 保科宏道
    第6回分子科学討論会  2012/09  東京大学 本郷キャンパス  第6回分子科学討論会
     
    発表番号1P049；
  • 森澤 勇介; 谷村恵里香; 佐藤春実; 尾崎幸洋; 苅山直美
    第6回分子科学討論会  2012/09  東京大学 本郷キャンパス  第6回分子科学討論会
     
    発表番号2P054；FUV領域(140-200 nm)には分子の許容電子遷移に相当する強い吸収が観測される。しかし、吸光係数が大きすぎ、これまで国内・国外において液体や固体のFUV領域の研究は限定的にしかされてこなかった。我々は測定部となる内部反射部材（IRE）から数十nm浸み出した光の吸収を測定するATR-FUV分光法を開発してきた。これまでの研究の中で、水、メタノール、アルカン、ケトンなど、これまで液体での研究が困難であった基本溶媒の電子状態研究を行ってきた。この中で、液体アルカンの電子励起状態への遷移に相当する吸収が、炭素数や枝分かれのような分子構造の違いにより変化することを示した。また、アルカンの固体相において液体とは大きく異なる吸収が観測されることも見出した。この研究から、（長鎖アルカンである）高分子などの骨格の構造変化によってそのスペクトルが変化すると予想される。 高分子の遠紫外スペクトルは、薄膜の透過スペクトルの報告があ
  • 和田資子; 若林 知成; 森澤 勇介
    第6回分子科学討論会  2012/09  東京大学 本郷キャンパス  第6回分子科学討論会
     
    発表番号1P082
  • 二見能資; 森澤 勇介; 尾崎裕; 濱田嘉昭; 尾崎幸洋
    第6回分子科学討論会  2012/09  東京大学 本郷キャンパス  第6回分子科学討論会
     
    発表番号1P071；
  • 無極性溶媒中におけるポリイン-ヨウ素錯体の赤外吸収スペクトル  [Not invited]
    和田 資子; 若林 知成; 森澤 勇介
    第43回 フラーレン・ナノチューブ・グラフェン 総合シンポジウム  2012/09  東北大学  第43回 フラーレン・ナノチューブ・グラフェン 総合シンポジウム
  • 谷村恵里香; 森澤 勇介; 佐藤春実; 苅山直美 東
    日本分析化学会第61年会  2012/09  金沢大学  日本分析化学会第61年会
     
    Ｄ2003；高分子の表面改質や表面装飾は、高分子材料の用途の広がりとともに、必然的に重要になってきた技術である。従来高分子の表面の官能基などの分子に関する情報を得る方法として減衰全反射（ATR)赤外(IR)分光法があるが、分析深さは数μmである。分析深さは波長に比例するので、遠紫外(FUV)領域では分析深さが数十nm程度となり、これまでに比べてはるかに薄い表面に局在した情報を分析できる。本研究では、固体極表面分析用ATR-FUV分光器を開発し、これを用いてポリエチレンの測定を行い、ATR-FUVスペクトルの変化について考察した。また、原子間力顕微鏡(AFM)を用いて、ポリエチレンの表面状態とスペクトルとの比較を行った。
  • 後藤剛喜; 森澤 勇介; 池羽田晶文; 東昇; 尾崎幸洋
    日本分析化学会第61年会  2012/09  金沢大学  日本分析化学会第61年会
     
    Ｄ2003；液体状態水分子の第一電子遷移(A-X)エネルギーは遠紫外領域(122~200 nm)に存在し, その電子遷移は水分子間の水素結合状態に強く依存している. これまで測定されたs, pブロック金属塩水溶液の減衰全反射遠紫外(ATR-FUV)スペクトルから, A？Xエネルギーはカチオンの水和状態に依存する傾向が分かっている.[1] 本研究では, その傾向の背景を明らかにすることを目的に, ATRスペクトル及び量子化学計算から液体水分子のA？Xを検討した.
  • 後藤剛喜; 森澤 勇介; 池羽田晶文; 苅山直美; 高場京子; 尾崎
    日本分析化学会第61年会  2012/09  金沢大学  日本分析化学会第61年会
     
    P3036；低ケミカルな洗浄プロセスとしてO3を主成分とする促進酸化水が半導体基板洗浄など多様な分野で用いられている. O3や過渡種であるOHラジカルは高い酸化力を有し, 多様な有機物の無機化に効果を示す. O3の光解離反応, ラジカル反応機構は複雑かつ多様であり, 様々なアプローチで研究が進められてきた. 本研究では, ポンプ-プローブ時間分解遠紫外透過分光法を用いて促進酸化水の光反応キネテックスの検討を行う
  • 森澤 勇介; 後藤剛喜; 東昇 苅山直美; 高場京子; 尾崎
    日本分析化学会第61年会  2012/09  金沢大学  日本分析化学会第61年会
     
    P3020；オゾン水に紫外線（266nm)を照射することで、溶液中でオゾンの光分解がおこることが知られている。生成されるのは小分子ラジカルであるため、既存の過渡吸収法では生成物の吸収を得ることは難しいと考えられる。一方、ラジカルを検出するために短波長側に測定を名橋た場合、水の強い吸収によって光を透過させることができないため、これまで測定が難しかった。我々は、独自に開発した減衰全反射遠紫外（ATR-FUV）分光法を用いて、短波長領域（本研究では170-185 nm）においても、吸収スペクトルを測定することができる。さらに、これにパルスレーザーの照射光学系と時間応答性の高い検出器を組み合わせ、50ns～1μsの時間分解能で0.001～0.0005abs程度の感度でFUV過渡吸収測定を可能にする時間分解ATR-FUVを開発した。本研究では、これを用いてオゾン水に紫外線を当てた時に生じる過渡種の検出を試みた。
  • 立花慎; 森澤 勇介; 苅山直美; 後藤剛喜; 高場京子; 尾崎
    RSC Tokyo International Conference, International Session, JASIS Conference  2012/09  幕張メッセ  RSC Tokyo International Conference, International Session, JASIS Conference
     
    In this study, we measured the photoreaction kinetics of O3 water by using the pump-probe style time-resolved far-ultraviolet (TR-FUV) spectrometer. The TR-FUV spectrometer is equipped with Nd:YAG laser (266 nm, 50 mJ/pulse) as a excitation pulse to start the photoreaction of O3. The laser driven Xe lamp source is employed as a probe light source. The probe light transmitting the sample is detected by photomultiplier (PMT) after through the spectrometer. The detected signal is collected by digital oscilloscope. Temporal resolution is determined by the response time of pre-amplifier as 50 ns. We measured 50 μs before and after pulse irradiation.
  • 森澤 勇介; 谷村恵里香; 佐藤春実; 尾崎幸洋; 苅山直美
    RSC Tokyo International Conference, International Session, JASIS Conference  2012/09  幕張メッセ  RSC Tokyo International Conference, International Session, JASIS Conference
     
    A technique for the surface analysis of polymers regarding molecular level is needed. ATR-IR spectroscopy has been widely used for surface analysis of polymers. In the measurement of ATR-IR, however, the depth of analysis is reached to several micrometers. In the far-UV region, transitions of the valence electrons have been observed in the liquid phase by using ATR-FUV spectroscopy. Because the penetration depth is proportional to the wavelength, it is tens of nanometers in the ATR-FUV measurement. Thus, if we applied the ATR-FUV to the polymers, one should be possible to obtain the information of electronic structure localized to the more extreme surface by using ATR-FUV. In this study, we originally developed FUV spectrometer for investigating extreme surface of polymers by using ATR technique. To test the instrument, we studied electronic state of several kinds of polyethylenes.
  • 保科宏道; 森澤 勇介; 石井伸也; 佐藤春実; 野田勇夫
    応用物理学会テラヘルツ電磁波研究会並びに電子情報通信学会テラヘルツ応用シス テム研究会共催「テラヘルツ電磁波研究会」  2012/07  独立行政法人 情報通信研究機構（NICT) 沖縄電磁波計測センター  応用物理学会テラヘルツ電磁波研究会並びに電子情報通信学会テラヘルツ応用シス テム研究会共催「テラヘルツ電磁波研究会」
  • 保科宏道; 森澤 勇介; 鈴木はる; 石井; 伸弥; 大谷知行; 山本茂樹; 佐藤春実; 尾崎幸洋; 内山哲治
    The 2nd International Symposium on Terahertz Nanoscience (TeraNano 2012)  2012/07  Okinawa Electromagnetic Technology Center, NICT, Okinawa, Japan  The 2nd International Symposium on Terahertz Nanoscience (TeraNano 2012)
  • 森澤 勇介
    日本分光学会  2012/06  島津製作所関西支社 マルチホール  日本分光学会
     
    田隅 三生 編著｢赤外分光測定法－基礎と最新手法｣発刊にともなって、日本分光学会が主催した講習会において、「近赤外分光法」に関する講師を務めた。講演では、当該冊子の内容に沿って、近赤外分光法の特徴と課題について解説を行った。
  • 保科宏道; 森澤 勇介; 大谷知行; 石井伸弥; 山本茂樹; 佐藤春実; 尾崎幸洋; 野田勇夫
    European Optical Society  2012/06  プラハ、チェコ共和国  European Optical Society
     
    プログラム P.23 （口頭発表） Vibrational spectra of poly-(3-hydroxybutyrate) (PHB) and nylon were studied by terahertz (THz) spectroscopy. The vibrational peaks of hydrogen bonds, which control the intermolecular structure, were observed. The correlation between THz spectra and higher order conformation of polymer was studied.
  • 森澤 勇介; 山本茂樹; 佐藤春実; 尾崎幸洋; 保科宏道
    European Optical Society  2012/06  プラハ、チェコ共和国  European Optical Society
     
    プログラム P.23 （口頭発表） Terahertz (THz) and low-frequency Raman spectra of poly(3-hydroxybutyrate) were compared with the DFT calculations with Cartesian coordinate tensor transfer method. Result of the calcula-tion agreed with both the THz and Raman spectra. Assignments of inter- and intramolecular vi-brational bands have been carried out.
  • 谷村恵里香; 立花慎; 佐藤春実; 尾崎幸洋; 森澤 勇介; 苅山直美; 東昇
    第72回分析化学討論会  2012/05  鹿児島  第72回分析化学討論会
     
    ポスター発表 Ｙ1015 要旨集p.130 【序論】近年、高分子の表面装飾や表面処理が注目を集めている。優れた表面の作製には、ナノメートルオーダーの物性や組成を分析することが有用である。従来高分子の表面を官能基レベルで分析する手法として用いられてきた減衰全反射(Attenuated Total Reflection、ATR)赤外(IR)分光法では、分析深さは数μmである。分析深さは波長に比例するので、遠紫外(FUV)領域では分析深さが数十nm程度となり、これまでに比べてはるかに薄い表面に局在した情報を分析できる。これまでの研究から、液体アルカンの炭素数や枝分かれの違いがスペクトルに変化をもたらす1)ということがわかっている。本研究では、固体極表面分析用ATR-FUV分光器を開発し、これを用いてポリエチレンの測定を行い、液体、固体アルカンとの比較から、ATR-FUVスペクトルの変化について考察した。 【実験】ATR-FUV測定装置は窒素パージ式で、光源には重水素ランプ、内部反射部材にはサフ
  • 森澤 勇介; 東昇; 苅山直美; 高場京子; 尾崎幸洋; 後藤剛喜; 池羽田晶文
    第72回分析化学討論会  2012/05  鹿児島  第72回分析化学討論会
     
    口頭発表 C1006 要旨集P33 減衰全反射遠紫外分光法（ATR-FUV）を用いることで、これまで水の強い吸収によって光を透過させることができなかった波長領域（本研究では170-185 nm）においても、吸収スペクトルを測定することができる。さらに、これにパルスレーザーの照射光学系と時間応答性の高い検出器を組み合わせることで、ATR-FUVのns～μs程度の時間分解能で過渡吸収測定を可能にする時間分解ATR-FUVを開発したことを第60年会で報告した。本討論会では、以前の発表では問題となっていた感度について、光学系および光源の改善により向上させた結果について報告する。 図は今回開発したATR-FUVによって得られた5mMフェノール水溶液に266 nmレーザー光照射後の172 nmにおける吸収信号の時間変化である。時間分解能はプリアンプの応答速度である50 ns程度であることが見積もられる。図に示されるようにフェノール水溶液に光を照射した直後に急激に吸光度が立ち上がり、それが1 μs程度
  • Expanding World of Vibrational Spectroscopy: Advances Brought by Ultra-Short Pulse Laser Light  [Invited]
    Yusuke Morisawa; Yukihiro Ozaki; Hiromichi Hoshina
    光学  2011/08
  • Akifumi Ikehata; Takeyoshi Goto; Yusuke Morisawa; Yukihiro Ozaki; Noboru Higashi
    Bunseki-kagaku  2011
  • Terahertz spectroscopy of poly(3-hydroxyalkanoate)s  [Not invited]
    Hoshina, Hiromichi; Morisawa, Yusuke; Ishii, Shinya; Sato, Hammi; Noda, Isao; Ozaki, Yukihiro; Otani, Chiko
    Annual Report - Conference on Electrical Insulation and Dielectric Phenomena  2011
  • Yusuke Morisawa
    分光研究  2006

MISC

Industrial Property Rights

Awards & Honors

  • 2022/06 The Japan Society for Analytical Chemistry Outstanding Reviewer Award in Analytical Sciences 2021
     JPN official_journal 
    受賞者: Yusuke MorisawaThis is to certify your great contribution to Analytical Sciences as a reviewer in 2021. This distinction was determined based on quantity, quality, and speed of reviews. We very much appreciate your further support for Analytical Sciences.
  • 2020/11 Japan Council Near Infrared Spectroscopy NIR Advanced Award
     "Study for effects of intermolecular interactions in solutions on absorption intensities in the NIR region" JPN japan_society 
    [1] “Effects of intermolecular interactions on absorption intensities of the fundamental and the first, second, and third overtones of OH stretching vibrations of methanol and t-butanol‑d 9 in n-hexane studied by visible/near-infrared/infrared spectroscopy.” Yusuke Morisawa, Arisa Suga, Spectrochimica Acta A., 197, 170– 175 (2018) [2] “Solvation effects on wavenumbers and absorption intensities of the OH-stretch vibration in phenoliccompounds – electrical- and mechanical anharmonicity via a combined DFT/Numerov approach.” Manuel J. Schuler, Thomas S. Hofer, Yusuke Morisawa, Yoshisuke Futami, Christian W. Huck, Yukihiro Ozaki, Physical Chemistry Chemical Physics, 22, 13017-13029 (2020)
  • 2013/11 日本分光学会 奨励賞
     「減衰全反射遠紫外分光法を用いた凝縮相分子の電子遷移の 研究とその装置開発」 
    受賞者: 森澤勇介
  • 2013/01 日本分析化学会近畿支部 近畿分析技術研究 奨励賞
     
    受賞者: 森澤勇介
  • 2011/09 日本分析化学会 先端分析技術賞・JAIMA機器開発賞
     
    受賞者: 尾崎幸洋;東昇;池羽田晶文;森澤勇介

Research Grants & Projects

  • Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2021/04 -2024/03 
    Author : 森澤 勇介
     
    本研究はハイドレートメルト (HM)での電位窓拡張機構の実証のために、電気化学的減衰全反射遠紫外分光法（EC-ATR-FUV）の多角入射測定により高濃度塩水溶液中の水の電子状態の変化を観測し、物性向上機構を解明することが目的である。令和3年度においては、電位窓拡張機構における水の電子状態の解明を目指し、既存のATR-FUV分光法を用いて水の高濃度塩水溶液中における水の電子状態変化の解明を目指した。 リチウム ビス（トリフルオロメタンスルホニル）イミド（LiTFSI）とリチウム ビス（ペンタフルオロエタンスルホニル）イミド（LiBETI）の混合塩と水をLiTFSI : LiBETI：H2O＝x：1-x：2.0のモル比（x=1.0~0.7）で混合した水溶液（Li-HM）と、LiBETIをリチウムトリフルオロスルメチルホン酸(LiTFS)に置換した水溶液および、これらリチウム塩単独の水溶液の濃度依存性を既存のATR-FUV分光器で測定した。その結果、水同士の水素結合と水とリチウムイオンの配位結合の割合によって、水の第一遷移エネルギー（HOMO-LUMOギャップに相当する）が高エネルギー側にシフトした。最も高濃度のLi塩溶液となるLi-HM中ではほとんどの水がリチウムと配位して、0.4eV以上大きくシフトすることを、はじめて実証した。これらの成果について3つの国際学会において発表し、1報の雑誌論文発表を行った。また、計画通りMgおよびNa塩についても濃度依存測定を開始した。マグネシウトリフルオロスルメチルホン酸（MgTFS）およびナトリウムトリフルオロスルメチルホン酸（NaTFS）について濃度測定を行った。これらの結果については、第82回分析化学討論会（2022年5月開催）にて口頭発表を予定している。
  • Nondestructive structural analysis of cellar biomolecules by ATR Far-UV spectroscopy - synchrotoron based tunable UV resonance Raman Spectroscopy
    JSPS：二国間交流事業（共同研究）
    Date (from‐to) : 2022/04 -2024/03 
    Author : Yusuke Morisawa; Hidetoshi Sato; Yukihiro Ozaki; Kosuke Hashimoto
  • 文部科学省：科学研究費補助金（基盤研究（A))
    Date (from‐to) : 2015/04 -2018/03 
    Author : 尾崎幸洋
  • 文部科学省：科学研究費補助金（基盤研究（C))
    Date (from‐to) : 2015/04 -2017/03 
    Author : 池羽田晶文
  • 文部科学省：科学研究費補助金（基盤研究（C))
    Date (from‐to) : 2015/04 -2017/03 
    Author : 松本浩一
  • Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2013/04 -2015/03 
    Author : MORISAWA Yusuke
     
    Electronic states of polystyren nano particle (PSNP) whose diameters are 50-500 nm and surface modificated PSNSP were observed by variable-incidence-angle (VIA) measurement of attenuated total reflectance spectroscopy in the far-ultraviolet region (ATR-FUV). The VIA-ATR-FUV has enabled us to measure the FUV spectra for solid samples without peak-saturation by nitrogen gas purge, and to study the variation in the depth from the surface. In order to arrange the PSNP on the surface with regularity, spin coater was used to form films. The spectra of spin-coated PSNP film could be measured with good reproducibility. It was found that PSNP with larger diameters than wavelength are strongly affected by the real part of refractive index, that is effect of scattering, on the other hand, the spectra of the smaller nano-particle was similar to that of the uniform PS film. The variation in the depth were analyzed by using FDTD method of electromagnetic wave.
  • 文部科学省：基盤研究(B)
    Date (from‐to) : 2011/04 -2014/03 
    Author : 尾崎幸洋
  • 文部科学省：化学研究費補助金（基盤（B）)
    Date (from‐to) : 2010/04 -2013/03 
    Author : 保科宏道
  • Japan Society for the Promotion of Science：Grants-in-Aid for Scientific Research
    Date (from‐to) : 2010 -2011 
    Author : MORISAWA Yusuke
     
    Effect of intermolecular interaction, such as hydrogen bonds and van der Waals forces to valence electrons were investigated by using an attenuated total reflection spectrometer in far-UV(ATR-FUV). After developing the ATR-FUV equipment for measurements in low temperature(～-70℃), ATR-FUV spectra of liquid acetone and, solid and liquid alkanes were observed. Comparing the results of electronic states in low-temperature liquids and high level quantum chemical calculations, we got a new insight about the effect of intermolecular interaction to valence electrons.

Social Contribution

  • 「赤外・近赤外分光法を用いたバイオコークスの表面構造変化に関する研究」
    Date (from-to) : 2021/07/15
    Role : Lecturer
    Sponser, Organizer, Publisher  : ブルカージャパン株式会社 オプティクス事業部
    Event, Program, Title : 赤外ラマン技術セミナー2021
    毎回大変ご好評を頂いておりますブルカー主催の「赤外・ラマン技術セミナー」を本年はオンライン方式で開催する運びとなりました。サブタイトルを「基礎と応用：赤外・ラマン有効活用のヒント」と題し、全６講演を３回に分けて配信いたします。最先端の研究開発の現場でご活躍中の６名の講師をお招きし、赤外・ラマンの分光学の基礎から最新の分析技術とデータ解析法、さらには活用におけるノウハウ等についてご講演を頂きます。この機会にぜひ多くの皆様にご視聴頂けますと幸いです。 ご参加をお待ちしておりますので、どうぞよろしくお願い申し上げます。 (担当は3日のうちの第3回）
  • ｢近赤外分光の基礎と応用｣
    Date (from-to) : 2020/11/17
    Role : Lecturer
    Category : Lecture
    Sponser, Organizer, Publisher  : 京都府中小企業技術センター、公益財団法人京都技術科学センター
    Event, Program, Title : ものづくり分析評価技術研究会
    ものづくりの現場では、紫外光や赤外光などの波長領域の異なる様々な光が、製品開発や品質管理などの分析に活用されていますが、どのような場合にどの波長領域の分析装置を選択するかは技術者を悩ませるところです。令和元年度に発足した本研究会は、府内中小企業の技術者の皆様に現場で活きる系統的な分光分析技術を学んでいただく場として、分光分野のトップランナーによる講演と分析装置の操作実習を行っています。(担当は３回のうちの第2回目）
  • Date (from-to) : 2019/10/09
    Role : Lecturer
    Category : Seminar
    Sponser, Organizer, Publisher  : 京都府中小企業技術センター、公益財団法人京都技術科学センター
    Event, Program, Title : ものづくり分析評価技術研究会
    ものづくり分析評価技術研究会
  • 遠紫外分光法の分光学的基礎、物理化学への応用
    Date (from-to) : 2014/11/20
    Role : Lecturer
    Category : Seminar
    Sponser, Organizer, Publisher  : オプトロニクス
    Event, Program, Title : 第2回分光フェア 分光セミナー

Academic Contribution

  • ラジカル測定用時間分解ATR-FUV分光システムの開発
    Date (from-to) :2010/09

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