First observation of a dihydrogen bond involving the Si-H group in phenol-diethylmethylsilane clusters by infrared-ultraviolet double-resonance spectroscopy

We have experimentally identified a dihydrogen bond involving the Si-H group in phenol-diethylmethylsilane (DEMS) clusters for the first time by IR-UV double-resonance spectroscopy. Vibrational shifts to lower frequency of 21-29 cm(-1) were found for the OH stretching vibration of three isomers of the phenol-DEMS clusters. Spectral simulations based on the MP2 calculations also support our observation. In addition to these clusters, dihydrogen bonds were also observed in the phenol-H(2)O-DEMS and (phenol)(2)-DEMS clusters, which exhibited much stronger interactions than the phenol-DEMS clusters.     

Vibrational dynamics of pyrrole via frequency-domain spectroscopy

The N-H stretch overtones of pyrrole, a key constituent of biologic building blocks, were studied by room temperature photoacoustic and jet-cooled action spectroscopies to unravel their intramolecular dynamics. Contrary to "isolated" states excited with two and three N-H stretch quanta, the one with four quanta shows strong accidental resonances with two other states involving three quanta of N-H stretch and one quantum of C-H stretch. The inhomogeneously reduced features in the action spectra provide the means for getting insight into the intramolecular interactions and the factors controlling energy flow within pyrrole. The time dependence of the survival probability of the 4ν(1) N-H stretch, deduced from the vibrational Hamiltonian, shows an initial decay in ~0.3 ps with ensuing quantum beats from the N-H-C-H resonance and their decay with a time constant of about 5 ps as a result of weaker coupling to bath states.     

Vibrational energy transfer in ozone by infrared-ultraviolet double resonance

Absorption transients at 254 nm have been observed in O₃-O₂ mixtures following laser irradiation at 9.64 μm. From analysis of these transients, we are able to determine vibrational relaxation rate constants (O₃-O₂ λ₁^?1/[O₂] = (2560±370) Torr^?1 S^?1, λ₂^?1/[O₂] = (640±50) Torr^?1 S^?1, and also a v₁-v₃ equilibration rate constant (O₃-O₃) of (1.5±1.0) × 10⁶ Torr^?1 S^?1.     

Vibrational overtone spectroscopy and intramolecular dynamics of ethene

The first through fourth C-H stretching overtone regions of ethene were measured by photoacoustic spectroscopy of room-temperature molecules and action spectroscopy of jet-cooled molecules. The rotational cooling led to improved resolution in the action spectra, turning these spectra into key players in determining the multiple band appearance in each region, their types, and origins. These manifolds arise from strong couplings of the C-H stretches to doorway states and were analyzed in terms of a simplified joint local-mode/normal-mode (LM)/(NM) model and an equivalent NM model, accounting for principal resonances. The diagonalization of the LM/NM and NM vibrational Hamiltonians and the least-square fittings revealed model parameters, enabling assignment of A- and B-type bands. These bands behave differently through the V = 2-4 manifolds, showing coupling to doorway states for the former but not for the latter. The energy flow out of the fourth C-H overtone is governed by the interaction with bath states due to the increase in the density of states.     

Vibrational spectroscopy and intramolecular dynamics of 1-butyne

Photodissociation of jet-cooled vibrationally excited 1-butyne, C(2)H(5)C[Triple Bond]C[Single Bond]H, coupled with mass spectrometric detection of H photofragments, facilitated measurements of action spectra and Doppler profiles, expressing the yield of the ensuing fragments versus the vibrational excitation and UV probe lasers, respectively. Both the action spectra and the simultaneously measured room temperature photoacoustic spectra in the 2nu(1), 3nu(1), and 4nu(1) C[Single Bond]H acetylenic stretch regions exhibit unresolved rotational envelopes with significant narrowing of the former due to temperature-related change in the rotational structure. The narrowing of the action spectrum in the 3nu(1) region exposed a resonance splitting, implying intramolecular vibrational energy redistribution (IVR) time of approximately 1 ps. Asymmetric rotor simulation of the band contours provided the rotational constants and estimates for the homogeneous broadening arising from IVR to the bath vibrational states. The homogenous linewidth of 4nu(1) is anomalously narrower than that of 2nu(1) and 3nu(1), indicating a longer lived 4nu(1) state despite the increasing background state density, suggestive of a lack of low-order resonances or of mode-specific coupling with the bath states. The Doppler profiles indicate that the H photofragments are released with low average translational energies, pointing to an indirect dissociation process occurring after internal conversion (IC) to the ground electronic state or after IC and isomerization to butadiene.     

Vibrational spectroscopy and dynamics of small anions in ionic liquid solutions

Fourier-transform infrared (FTIR) and time-resolved IR spectroscopies have been used to study vibrational band positions, vibrational energy relaxation (VER) rates, and reorientation times of anions in several ionic liquid (IL) solutions. The ILs primarily investigated are based on the 1-butyl-2,3-dimethylimidazolium ([BM(2)IM]) cation with thiocyanate (NCS-), dicyanamide (N(CN)2-), and tetrafluoroborate (BF4-) anions. Spectroscopic studies are carried out near 2000 cm-1 for the C[Triple Bond]N stretching bands of NCS- and N(CN)2- as the IL anion as well as for NCS-, N(CN)2-, and azide (N3-) anions dissolved in [BM2IM][BF4]. The VER studies of N(CN)2- are reported for the first time. VER of N3-, NCS-, and N(CN)2- is measured in normal solvents, such as N-methylformamide, to compare with the IL solutions. The spectral shifts and VER rates of the anions in IL solution are quite similar to those in polar aprotic, conventional organic solvents, i.e., dimethylsulfoxide, and significantly different than those in methanol, in which there is hydrogen bonding. Similar studies were also carried out for the anions in another IL, 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), in which the C2 hydrogen is present. The results for the anions are similar to those in the [BM2IM] containing ILs, in which the C2 hydrogen is methyl substituted. This suggests that substituting this hydrogen has, at most, a minor effect on the degree of hydrogen bonding in the anion-IL solvation interaction based on the infrared spectra and dynamics.     

Infrared double-resonance spectroscopy of bromoform with picosecond pulses

Using independently tunable pump and probe pulses in the infrared, time- and frequency-resolved spectroscopy of vibrationally excited, polyatomic molecules in liquids is demonstrated for the first time. Experimental data are presented for CHBr₃, measuring the population lifetime via excited-state absorption of the CH-stretching mode; for larger probe delay, the non-equilibrium population of intermediate vibrational levels in the relaxation ladder of bromoform is observed.     

Structure of the phenylacetylene-water complex as revealed by infrared-ultraviolet double resonance spectroscopy

The structure of the phenylacetylene-water complex has been elucidated based on spectral shifts in electronic and vibrational transitions. Phenylacetylene forms a cyclic complex with water incorporating C-H...O and O-H...pi hydrogen bonds, which is different from both the benzene-water and acetylene-water complexes, even though phenylacetylene combines the features of both benzene and acetylene. Formation of such a complex can be rationalized on the basis of cooperativity between the two sets of hydrogen bonds.     

Vibrational spectroscopy of resveratrol

In this article the authors deal with the experimental and theoretical interpretation of the vibrational spectra of trans-resveratrol (3,5,4'-trihydroxy-trans-stilbene) of diverse beneficial biological activity. Infrared and Raman spectra of the compound were recorded; density functional calculations were carried out resulting in the optimized geometry and several properties of the molecule. Based on the calculated force constants, a normal coordinate analysis yielded the character of the vibrational modes and the assignment of the measured spectral bands.     

Vibrational spectroscopy of implants

The results of systematic spectral studies of polymers in ophthalmology are presented. The spectral criteria of selection of intraocular lens (IOL; implants of long service in an organism have been defined for poly(methylphenylsiloxane). Non-inflammatory implantation of IOL, when the manufacturing of lenses is performed under spectral control at several stages, has been realized. New siloxane–polyurethane block copolymers promising for ophthalmology have been studied and passivated surfaces have been obtained.     

Vibrational spectroscopy of N-phenylmaleimide

A combination of infrared, Raman and inelastic neutron scattering (INS) spectroscopies with density functional theory (DFT) calculations is used to provide a complete assignment of the vibrational spectra of N-phenylmaleimide and N-(perdeuterophenyl)maleimide. DFT is shown to give very good results for the frequencies and atomic displacements in the modes. These are used to generate INS spectra which are excellent agreement with the observed. The calculated infrared and Raman spectra are much less reliable, although this may be more of a presentation problem than a real failing.     

Vibrational spectroscopy of stichtite

Raman spectroscopy complimented with infrared spectroscopy has been used to study the mineral stitchtite, a hydrotalcite of formula Mg6Cr2(CO3)(OH)16.4H2O. Two bands are observed at 1087 and 1067 cm(-1) with an intensity ratio of approximately 2.5/1 and are attributed to the symmetric stretching vibrations of the carbonate anion. The observation of two bands is attributed to two species of carbonate in the interlayer, namely weakly hydrogen bonded and strongly hydrogen bonded. Two infrared bands are found at 1457 and 1381 cm(-1) and are assigned to the antisymmetric stretching modes. These bands were not observed in the Raman spectrum. Two infrared bands are observed at 744 and 685 cm(-1) and are assigned to the nu4 bending modes. Two Raman bands were observed at 539 and 531 cm(-1) attributed to the nu2 bending modes. Importantly the band positions of the paragenically related hydrotalcites stitchtite, iowaite, pyroaurite and reevesite all of which contain the carbonate anion occur at different wavenumbers. Consequently, Raman spectroscopy can be used to distinguish these minerals, particularly in the field where many of these hydrotalcites occur simultaneously in ore zones.     

Vibrational vave-packet dynamics in CV670 investigated by broadband femtosecond TR-CARS spectroscopy

Broadband femtosecond time-resolved coherent anti-Stokes Raman scattering ((TR-CARS)) is utilized to investigate the wave-packet dynamics of Cresyl Violet (CV670) dye molecules in ethanol solvent at room temperature. An interesting behavior of wave-packet dynamics phenomena is observed and discussed for the first time, and several unknown Raman vibrational modes with frequency differences of 32 cm⁻¹, 38 cm⁻¹, 45 cm⁻¹, 50 cm⁻¹, 55 cm⁻¹, 65 cm⁻¹, 80 cm⁻¹, 95 cm⁻¹ and 101 cm⁻¹ are excited and obtained at the same time. This work makes possible high efficiency in the structure investigation as well as dynamics of intra-molecular processes by broadband femtosecond (TR-CARS) spectroscopy with fast Fourier transformation (FFT) analysis means.     

Vibrational spectroscopy and dynamics in the CH-stretch region of fluorene by IVR-assisted, ionization-gain stimulated Raman spectroscopy

We report stimulated Raman spectra at 0.2 and 0.03 cm(-1) resolution in the CH-stretching region of jet-cooled fluorene. The results were obtained by a version of ionization-gain stimulated Raman spectroscopy in which resonant two-photon ionization probing of the state-population changes arising from stimulated Raman transitions is assisted by the process of intramolecular vibrational redistribution (IVR) in the Raman-excited molecule. The fluorene spectra reveal extensive vibrational coupling interactions involving both the aliphatic and aromatic CH-stretching first excited states with nearby background states. Results pertaining to the symmetric aliphatic CH-stretching fundamental are consistent with a tier model of IVR and point to vibrational energy flow out of the CH stretch on a approximately 1 ps time scale with subsequent redistribution on a approximately 5 ps time scale.     

Vibrational dynamics of acetate in D2O studied by infrared pump-probe spectroscopy

Solute-solvent interactions between acetate and D(2)O were investigated by vibrational spectroscopic methods. The vibrational dynamics of the COO asymmetric stretching mode in D(2)O was observed by time-resolved infrared (IR) pump-probe spectroscopy. The pump-probe signal contained both decay and oscillatory components. The time dependence of the decay component could be explained by a double exponential function with time constants of 200 fs and 2.6 ps, which are the same for both the COO asymmetric and symmetric stretching modes. The Fourier spectrum of the oscillatory component contained a band around 80 cm(-1), which suggests that the COO asymmetric stretching mode couples to a low-frequency vibrational mode with a wavenumber of 80 cm(-1). Based on quantum chemistry calculations, we propose that a bridged complex comprising an acetate ion and one D(2)O molecule, in which the two oxygen atoms in the acetate anion form hydrogen bonds with the two deuterium atoms in D(2)O, is the most stable structure. The 80 cm(-1) low-frequency mode was assigned to the asymmetric stretching vibration of the hydrogen bond in the bridged complex.     

Vibrational spectroscopy of nitroalkane chains using electron autodetachment and ar predissociation

If the binding energy of an excess electron is lower than some of the vibrational levels of its host anion, vibrational excitation can lead to autodetachment. We use excitation of CH stretching modes in nitroalkane anions (2700-3000 cm(-1)), where the excess electron is localized predominantly on the NO2 group. We present data on nitroalkane anions of various chain lengths, showing that this technique is a valid approach to the vibrational spectroscopy of such systems extending to nitroalkane anions at least the size of nitropentane. We compare spectra taken by using vibrational autodetachment with spectra obtained by monitoring Ar evaporation from Ar solvated nitroalkane anions. The spectra of nitromethane and nitroethane are assigned on the basis of ab initio calculations with a detailed analysis of Fermi resonances of CH stretching fundamentals with overtones and combination bands of HCH bending modes.     

Vibrational spectroscopy of ion-irradiated ices

In the last 20 years we have studied some effects induced by fast ions (E approximately keV-MeV) impinging on solid materials (mainly ices) with a view to their astrophysical relevance. The main techniques used have been infrared and Raman spectroscopy. Here we review some of the results obtained so far concerning, in particular, the formation of new species not present in the original sample. When hydrocarbons are an important constituent of the target ion irradiation gives rise also to a refractory residue which is left over after warming up. In addition we present some preliminary results of a new study, still in progress, on the infrared properties of the organic residue formed after irradiation of an icy mixture with H-, C-, N- and O-bearing species. Furthermore we present the micro-Raman spectra of some fragments of Orgueil a carbonaceous chondrite meteorite. Some astrophysical applications of these laboratory results are also discussed.     

Vibrational spectroscopy of formamide-intercalated kaolinites

The vibrational spectroscopy of low and high defect kaolinites fully and partially intercalated with formamide have been determined using a combination of X-ray diffraction, DRIFT and Raman spectroscopy. Expansion of the high defect kaolinite to 10.09 A resulted in a decrease in the peak width of the d(001) peak attributed to a decrease in defect structures upon intercalation. Changes in the defect structures of the low defect kaolinite were observed. Additional infrared bands were observed for the formamide intercalated kaolinites at 3629 and 3606 cm(-1). The 3629 cm(-1) band is attributed to the hydroxyl stretching frequency of the inner surface hydroxyl group hydrogen bonded to the carboxyl group of the formamide. The 3606 cm(-1) band is ascribed to water in the interlayer. Concomitant changes are observed in both the hydroxyl deformation modes and in the carboxyl bands.