Study of first electronic transition and hydrogen bonding state of ultra-thin water layer of nanometer thickness on an α-alumina surface by far-ultraviolet spectroscopy.

The first electronic transition (A˜←X˜) and the hydrogen bonding state of an ultra-thin water layer of nanometer thickness between two α-alumina surfaces (0.5-20nm) were studied using far-ultraviolet (FUV) spectroscopy in the wavelength range 140-180nm. The ultra-thin water layer of nanometer thickness was prepared by squeezing a water droplet (~1µL) between a highly polished α-alumina prism and an α-alumina plate using a high pressure clamp (~4.7MPa), and the FUV spectra of the water layer at different thicknesses were measured using the attenuated total reflection method. As the water layer became thinner, the A˜←X˜ bands were gradually shifted to higher or lower energy relative to that of bulk water; at thicknesses smaller than 4nm, these shifts were substantial (0.1-0.2eV) in either case. The FUV spectra of the water layer with thickness <4nm indicate the formation of structured ice-like hydrogen bond (H-bond) layers for the higher energy shifts or the formation of slightly weaker H-bond layers as compared to those in the bulk liquid state for lower energy shifts. In either case, the H-bond structure of bulk liquid water is nearly lost at thicknesses below 4nm, because of steric hydration forces between the α-alumina surfaces.

Interpretation of the à ← X[combining tilde] transition of hydrated protons in aqueous solutions observed in the far-UV region with quantum chemical calculations.

Far-ultraviolet spectra (wavelength: 140-200 nm) of group I, II, and XIII cation nitrate electrolyte aqueous solutions show that the first electronic transition (à ← X[combining tilde]) energies of water hydrating the cations are linearly dependent on the hydration energies of the cations. However, deviations from these linear relations have been observed only for electrolyte solutions of small cations, i.e., H+, Li+, and Be2+ (T. Goto, A. Ikehata, Y. Morisawa, N. Higashi and Y. Ozaki, Phys. Chem. Chem. Phys., 2012, 14, 8097-8104). In this study, the à ← X[combining tilde] transitions of group I cation-water clusters holding the first and second shell water molecules around the cations (M+(H2O)6, M+: H+, Li+, Na+, and K+) were studied with quantum chemical calculations to elucidate the cation size effects on the electronic states of each shell water molecule. The calculation results show that the à ← X[combining tilde] transitions of the small cation clusters, especially H+, are more intensely split than those of the larger cation clusters, because of the difference in the à ← X[combining tilde] transition of each shell and the asymmetric structure of H+(H2O)6. Specifically, the à ← X[combining tilde] transitions of the first shell water molecules are mostly ascribed to the charge transfer transition of the nonbonding electrons to the central cations, while those of the second shell water molecules are ascribed to the transition to the σ* orbitals of the second shell water molecules. Moreover, the condensed and distorted structure of H+(H2O)6 causes an asymmetrically delocalized electronic distribution in the excited state, as well as the ground state, because the electronic interference from the second shell water molecules weakens the exciton-hole interaction of the first shell. These interpretations based on calculations provide a detailed explanation concerning the substantial blue-shift of the à ← X[combining tilde] band of aqueous sulfuric acid solutions.

Far- and deep-ultraviolet surface plasmon resonance sensors working in aqueous solutions using aluminum thin films.

Surface plasmon resonance (SPR) sensors detect refractive index changes on metal thin films and are frequently used in aqueous solutions as bio- and chemical-sensors. Recently, we proposed new SPR sensors using aluminum (Al) thin films that work in the far- and deep-ultraviolet (FUV-DUV, 120-300 nm) regions and investigated SPR properties by an attenuated total reflectance (ATR) based spectrometer. The FUV-DUV-SPR sensors are expected to have three advantages compared to visible-SPR sensors: higher sensitivity, material selectivity, and surface specificity. However, in this study, it was revealed that the Al thin film on a quartz prism cannot be used as the FUV-DUV-SPR sensor in water solutions. This is because its SPR wavelength shifts to the visible region owing to the presence of water. On the other hand, the SPR wavelength of the Al thin film on the sapphire prism remained in the DUV region even in water. In addition, the SPR wavelength shifted to longer wavelengths with increasing refractive index on the Al thin film. These results mean that the Al thin film on the sapphire prism can be used as the FUV-DUV-SPR sensor in solutions, which may lead to the development of novel and sophisticated SPR sensors.

A Correction Method for Attenuated Total Reflection-Far Ultraviolet Spectra Via the Use of Charge Transfer to Solvent Band Intensities of Iodide in the Ultraviolet Region.

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.

Direct optical measurements of far- and deep-ultraviolet surface plasmon resonance with different refractive indices.

The surface plasmon resonance (SPR) of Al thin films was investigated by varying the refractive index of the environment near the films in the far-ultraviolet (FUV, 120-200 nm) and deep-ultraviolet (DUV, 200-300 nm) regions. An original FUV-DUV spectrometer that adopts an attenuated total reflectance (ATR) system was used. The measurable wavelength range was down to the 180 nm, and the environment near the Al surface could be controlled. The resultant spectra enabled the dispersion relationship of Al-SPR in the FUV and DUV regions to be obtained. In the presence of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) on the Al film, the angle and wavelength of the SPR became larger and longer, respectively, compared to those in air. These shifts correspond well with the results of simulations performed using Fresnel equations.

Imaging of Hydrophilicity and its Inhomogeneity on a Titanium Dioxide Film Exposed to Ultraviolet Irradiation Using a Newly Developed Near-Infrared Camera.

This study has investigated hydrophilicity changes and their inhomogeneity of TiO2 films on Pyrex glasses by near-infrared (NIR) spectral imaging. Near-infrared spectra of TiO2 films in the 9000-4000 cm(-1) region were measured using a newly developed NIR camera named Compovision. A band in the 5400-4800 cm(-1) region, which is assigned to a combination (ν2 + ν3) mode of bending (ν2) and antisymmetric stretching (ν3) modes of the H2O molecule, was clearly identified and its intensity increased with time in the air. It is interesting that the increased rate rose with ultraviolet (UV) light irradiation (300-400 nm, 1 mW cm(-2)) compared to without UV light irradiation. This result suggested that the hydrophilicity of TiO2 was enhanced about twice upon the UV light irradiation. Moreover, the NIR images clarified spatial distributions of the hydrophilicity on the TiO2 surface with a significantly wide area (20 × 40 mm) and a high speed (within 5 s for one image). This rapid imaging system enabled us to detect the hydrophilicity change during only 1 min. The potential of this camera is quite superior, not only for basic research, but also for diverse industrial applications.

Surface Effect of Alumina on the First Electronic Transition of Liquid Water Studied by Far-Ultraviolet Spectroscopy.

The first electronic transition (à ← X̃) of liquid water (H2O and D2O) on an α-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 nm) 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 à ← X̃ 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.

Pulse laser photolysis of aqueous ozone in the microsecond range studied by time-resolved far-ultraviolet absorption spectroscopy.

Chemical dynamics of an ozone (O3) 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 O3 aqueous solutions (78-480 µM, pH 2.5-11.3) were acquired in the time range from -50 to 50 µs 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 µs of the constituted chemicals on the initial concentration of O3, it was found that the transient spectra involve the decomposition of O3 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 O3 concentration depends on the pH conditions from -0.95 to -0.60 for O3, 0.98 to 1.2 for H2O2, 0.002 to 0.29 for OH, and 0.012 to 0.069 for HO2.

Electronic transitions of protonated and deprotonated amino acids in aqueous solution in the region 145-300 nm studied by attenuated total reflection far-ultraviolet spectroscopy.

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.

Effects of lanthanoid cations on the first electronic transition of liquid water studied using attenuated total reflection far-ultraviolet spectroscopy: ligand field splitting of lanthanoid hydrates in aqueous solutions.

The effects of the lanthanoid cations (Ln(3+)) on the first electronic transition (à ← X̃) of liquid water were studied from the attenuated total reflection far-ultraviolet (ATR-FUV) spectra of trivalent Ln(3+) electrolyte solutions (1 M), except Pm(3+). The à ← X̃ 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 à ← X̃ transition energies decrease from La(3+) (4f(0), 8.0375 eV) to Nd(3+) (4f(3), 8.0277 eV) and increase from Sm(3+) (4f(5), 8.0279 eV) to Gd(3+) (4f(7), 8.0374 eV). For the complete occupation period, there are two local minima at Dy(3+) (4f(9), 8.0349 eV) and Yb(3+) (4f(13), 8.0355 eV). The à ← X̃ transition energies of the tetrad nodes (La(3+), Gd(3+), Ho(3+) (4f(10)), and Lu(3+) (4f(14))) increase slightly, as the nuclear charge increases in accordance with the hydration energies of the Ln(3+) cations. The energy difference (ΔE) between the à ← X̃ transition energies and the line between La(3+) and Lu(3+) is largest at Nd(3+) (80.5 cm(-1)) for the half occupation period and at Dy(3+) (26.1 cm(-1)) and Yb(3+) (24.5 cm(-1)) for the complete occupation period. The order of magnitude of ΔE is comparable to the ligand field splitting (LFS) of the ground state multiplets of Ln(3+) complexes. The observed tetrad trend of the à ← X̃ 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.

Development of a time-resolved attenuated total reflectance spectrometer in far-ultraviolet region.

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 π-π∗ 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.

The effect of metal cations on the nature of the first electronic transition of liquid water as studied by attenuated total reflection far-ultraviolet spectroscopy.

The first electronic transition (Ã←X̃) 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 Ã←X̃ 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 Ã←X̃ 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 Be(2+), which reflects that the electronic energies in the excited states are also perturbed. Quantum chemical calculations show that the Ã←X̃ transition energies of the water-cation complexes depend on the hydration structures of the cations. The calculated Ã←X̃ 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 Ã←X̃ transition bands measured by ATR-FUV spectroscopy.

SERS measurements of magnetic stretching force-induced trans-gauche conformational change.

The effects of stretching forces on covalently bridged 3-mercaptopropanoic acid molecules between magnetic particles (MPs) and Ag nano-particles (NPs) were studied by surface-enhanced Raman scattering (SERS) spectroscopy. With an exertion of 100 pN per single MP, the intensity ratio of the C-S stretching vibrations for trans-to-gauche conformations was increased from 0.295 +/- 0.008 to 0.69 +/- 0.09. From the experimental result, it was concluded that the magnetic forces increased the distance between the MP and the Ag NP surface, and induced a shift of the isomerization equilibrium to the trans conformation. The present approach is a new candidate for a dynamic force spectroscopy of conformational equilibria.

SERS study of rotational isomerization of cysteamine induced by magnetic pulling force.

The effects of unidirectional pulling forces on covalently bridged cysteamine between superparamagnetic particles and Ag nanoparticles (NPs) were studied with SERS spectroscopy. With an increase in the pulling force from 0 to 100 pN per magnetic particle, the nu(C-S)(Trans)/nu(C-S)(Gauche) intensity ratio was increased from 0.6 to 1.08, the Raman frequency of nu(C-S)(Trans) was shifted from 716 to 719 cm(-1), and the Raman bands associated with the amide groups were diminished. From these observations, it was concluded that the magnetic forces induced the extension of distance between the magnetic particle surface and the Ag NP surface and the rotational isomerization equilibrium of SC-CN was shifted from the gauche to the trans conformation with the longer molecular length.

Effects of a magnetic force on surface-enhanced Raman spectra of a cysteamine linking magnetic particle and a silver colloid plate.

The effects of a magnetic force on magnetic particles linked by cysteamine to a silver colloid plate were analyzed with surface-enhanced Raman scattering spectroscopy. Cysteamine molecules were stretched by a force exerted on the magnetic particles with the external magnetic field gradients generated by two Nd-Fe-B magnets. The spectra showed that the relative intensity ratio of C-S (trans) to C-S (gauche) of cysteamine was increased 2 - 3 times within 30 min under the application of magnetic field gradients. Also, the shift of C-S (T) was observed up to 4 cm(-1) to higher frequency. These results suggested that an extension of the distance between a magnetic particle and a silver colloid induced isomerization from the gauche conformation to the trans conformation, accompanied by probable thiolate migration on the silver colloid surface.

Raman microprobe spectrometer installed in a super-conducting magnet.

A Raman microprobe spectrometer that could be installed in the bore of a cryogen free super-conducting magnet (10 T) was designed and constructed for the investigation of the external magnetic field effect on the Raman spectra of molecular aggregates in solutions and at interfaces. The performance of the present instrument was demonstrated by measuring the magnetic field effect (0 - 10 T) on the resonance Raman spectra of diprotonated meso-tetra-(sulfonatophenyl)porphine aggregates in an acidic solution. The Raman shifts of the aggregates were not significantly influenced even in 10 T. However, the relative intensity of 1123 cm(-1) peak (nu(C(a)-N)) was interestingly enhanced about 20% under the magnetic fields higher than 2.5 T.