We investigated the optical properties of isolated single aggregates of Ag nanoparticles (Ag nanoaggregates) on which rhodamine 6G molecules were adsorbed to reveal experimentally a correlation among plasmon resonance Rayleigh scattering, surface-enhanced resonance Raman scattering (SERRS), and its background light emission. From the lack of excitation-laser energy dependence of background emission maxima we concluded that the background emission is luminescence, not Raman scattering. The polarization dependence of both SERRS and background emission was the same as that of the lowest-energy plasmon resonance maxima, which is associated with a longitudinal plasmon. From the common polarization dependence, we identified that the lowest-energy plasmon is coupled with both SERRS and background emission. In addition, we revealed that the lowest-energy plasmon with a higher quality factor (Q factor) yields larger SERRS and background emission intensity. Also, we identified that the Q factor dependence of the SERRS intensity was similar to that of the background emission intensity. This similarity directly supported us to demonstrate an enhancement of both SERRS and background emission by coupling with a common plasmon radiative mode.

Absorption bands of the first electronic transition (X (1)A(1)-->A (1)B(1)) of water (H(2)O) and heavy water (D(2)O) in the liquid state have been directly observed by using a uniquely designed attenuated total reflectance far-ultraviolet (ATR-FUV) spectrometer. Since the ATR geometry reduces the absorbance, the FUV spectra can be obtained over the entire X (1)A(1)-->A (1)B(1) absorption band, including the band maxima. Systematic measurements of the FUV spectra of H(2)O and D(2)O with heating from 10 to 70 degrees C and the analysis of Kramers-Kronig transformation reveal that the first electronic transition band redshifted on heating. This result is in good agreement with the redshift that has been frequently observed in the low-energy band tail of the X (1)A(1)-->A (1)B(1) absorption band.

An ultraviolet spectrometer based on attenuated total reflection (ATR) has been developed and tested for liquid water (light and heavy water) in the wavelength range from 140 to 300 nm, which includes the far ultraviolet (FUV) region. One of the principal limitations of FUV transmission spectra is the strong absorption of the solvent itself. High absorptivity of the n --> sigma(*) transition in water molecule has thus far prevented meaningful spectral measurements of aqueous solutions in the wavelength region under 170 nm. Our technique uses the evanescent wave created through total reflection when light is passed through an internal reflection element (IRE) in contact with the sample. Since the evanescent field is used as an optical path length, the method allows spectral measurements favorably comparable with that of transmittance method with a shorter path length than the wavelength of FUV light. In this study, we have designed an original miniature IRE probe made of sapphire that allows detection of the whole n --> sigma(*) transition absorption band of water down to 140 nm. The obtained ATR-FUV spectra closely match calculations based on the Fresnel formula. It is also confirmed that this spectrometer is equally effective for spectral measurements of nonaqueous solvents with significant absorptivities in the FUV region.

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.

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 of 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.