Vibrational relaxation of the H2O bending mode in liquid water

We have studied the vibrational relaxation of the H(2)O bending mode in an H(2)O:HDO:D(2)O isotopic mixture using infrared pump-probe spectroscopy. The transient spectrum and its delay dependence reveal an anharmonic shift of 55+/-10 cm(-1) for the H(2)O bending mode, and a value of 400+/-30 fs for its vibrational lifetime.     

Vibrational energy pathways in N2O

In previous papers a method has been proposed to find out the relative importance of the different paths in the decay of the ν₃ mode of N₂O, but the VT transfer constants involved in the kinetic model were barely known. As new values of VT constants have just been measured, the calculations of the kinetic model have been performed again; they qualitatively confirm the results already obtained with estimated VT constants.     

Vibrational energy relaxation at surfaces: O2 chemisorbed on Pt(111)

It is shown that the O-O stretch for O₂ chemisorbed on Pt(111) is likely to be damped via excitation of electron-hole pairs. Vibrational spectroscopic data for this system are analyzed using a model which assumes an adsorbate-induced resonance in the vicinity of the Fermi energy. In accordance with theory, the vibrational line profile is asymmetric and from the deduced linewidth γ, asymmetry parameter τ and vibrational polarizability α_v, we estimate the magnitude of the electron-phonon coupling parameter and derive information as to the nature of the adsorbate-induced resonance state.     

Vibrational partition functions for H2O derived from perturbation-theory energy levels

Purely vibrational energy levels and partition functions are calculated using three different potential energy surfaces for the H₂O molecule. Results obtained with perturbation-theory, independent-normal-mode (INM), and harmonic approximations are compared with accurate values. For the cases considered here, the expected improvement that perturbation theory provides over the corresponding harmonic treatment is found to be substantial, while the INM approximation leads to results which are worse than the corresponding harmonic ones. In fact, we show that reliable partition functions for these potential surfaces can be obtained when resonance contributions are removed from the perturbation-theory treatment, and we propose a theoretical criterion for deciding when a particular interaction should be treated as resonant.     

Vibrational energy relaxation rates of H2 and D2 in liquid argon via the linearized semiclassical method

The vibrational energy relaxation (VER) rates for H2 and D2 in liquid argon (T=152 K, rho=1.45x1022 cm-3) are calculated using the linearized semiclassical (LSC) method (J. Phys. Chem. 2003, 107, 9059, 9070). The calculation is based on Fermi's golden rule. The VER rate constant is expressed in terms of the quantum-mechanical force-force correlation function, which is then estimated using the LSC method. A local harmonic approximation (LHA) is employed in order to compute the multidimensional Wigner integrals underlying the LSC approximation. The H2-Ar and D2-Ar interactions are described by the three-body potential of Bissonette et al. (J. Phys. Chem. A 1996, 105, 2639). The LHA-LSC-based VER rate constants for both D2 and H2 are found to be about 2-3 orders of magnitude slower than those obtained experimentally. However, their ratio agrees quantitatively with the corresponding experimental result. In contrast, the classical VER rate constants are found to be 8-9 orders of magnitude slower than those obtained experimentally, and their ratio is found to be qualitatively different from the corresponding experimental result.     

Vibrational energy relaxation in liquid N2CO mixtures

The vibrational energy relaxation rates of the liquid nitrogenCO system have been measured by optically pumping the collision-induced fundamental vibrational absorption band of liquid N₂ with the output of an HBr TEA laser. A radiatively dominated value of 56 ± 10 s is found for the intrinsic nitrogen relaxation time. The CO contribution to the decay rate is explained on the basis of a simple kinetic model and found also to be radiatively dominated at low CO concentrations. The importance of radiative trapping and energy transport in evaluating the lifetimes is demonstrated.     

Vibrational relaxation of methane by oxygen collisions: measurements of the near-resonant energy transfer between CH4 and O2 at low temperature

Vibrational relaxation in methane-oxygen mixtures has been investigated by means of a time-resolved pump-probe technique. Methane molecules are excited into selected rotational levels by tuning the pump laser to 2nu3 lines. The time evolution in population of various vibrational levels after the pumping pulse is monitored by probing, near 3000 cm-1, stretching transitions between various polyads like 2nu3(F2) - nu3, (nu3+2nu4) - 2nu4, and (nu3+nu4) - nu4 transitions. Measurements were performed from room temperature down to 190 K. A numerical kinetic model, taking into account the main collisional processes connecting energy levels up to 6000 cm(-1), has been developed to describe the vibrational relaxation. The model allows us to reproduce the observed signals and to determine rate coefficients of relaxation processes occurring upon CH4-O2 collisions. For the vibrational energy exchange, the rate coefficient of transfer from O2 (v = 1) to CH4 is found equal to (1.32 +/- 0.09) x 10(-12) cm3 molecule-1 s(-1) at 296 K and to (1.50 +/- 0.08) x 10(-12) cm3 molecule(-1) s(-1) at 193 K.     

Vibrational energy relaxation of liquid deuterium chloride

The vibrational lifetime of DCI molecules has been measured in the liquid phase along the liquid—vapor coexistence curve. The results show that rotation plays an important role in vibrational relaxation of hydrogen halide liquids. They also substantiate the interpretation in terms of the role of vibrational predissociation of dimers.     

Vibrational energy relaxation of large-amplitude vibrations in liquids

Given the limited intermolecular spaces available in dense liquids, the large amplitudes of highly excited, low frequency vibrational modes pose an interesting dilemma for large molecules in solution. We carry out molecular dynamics calculations of the lowest frequency ("warping") mode of perylene dissolved in liquid argon, and demonstrate that vibrational excitation of this mode should cause identifiable changes in local solvation shell structure. But while the same kinds of solvent structural rearrangements can cause the non-equilibrium relaxation dynamics of highly excited diatomic rotors in liquids to differ substantially from equilibrium dynamics, our simulations also indicate that the non-equilibrium vibrational energy relaxation of large-amplitude vibrational overtones in liquids should show no such deviations from linear response. This observation seems to be a generic feature of large-moment-arm vibrational degrees of freedom and is therefore probably not specific to our choice of model system: The lowest frequency (largest amplitude) cases probably dissipate energy too quickly and the higher frequency (more slowly relaxing) cases most likely have solvent displacements too small to generate significant nonlinearities in simple nonpolar solvents. Vibrational kinetic energy relaxation, in particular, seems to be especially and surprisingly linear.     

Vibrational energy transfer in methanol and deuterated methanols

The vibrational energy transfer probabilities in methanol and deuterated methanols are calculated by Schwartz, Slawsky and Herzfeld breathing-sphere theory in the temperature range 300–1000 K. The required breathing-sphere parameters are obtained through normal coordinate analysis. All the modes of a manifold, either low-lying or upper vibrational levels, are coupled through rapid V-V exchange processes, whereas the cross-coupling transition probabilities between levels in the different manifolds are smaller by several orders of magnitude.     

Vibrational energy relaxation of small molecules and ions in liquids

A theoretical/computational framework for determining vibrational energy relaxation rates, pathways, and mechanisms, for small molecules and ions in liquids, is presented. The framework is based on the system—bath coupling approach, Fermi’s golden rule, classical time-correlation functions, and quantum correction factors. We provide results for three specific problems: relaxation of the oxygen stretch in neat liquid oxygen at 77 K, relaxation of the water bend in chloroform at room temperature, and relaxation of the azide ion anti-symmetric stretch in water at room temperature. In each case, our calculated lifetimes are in reasonable agreement with experiment. In the latter two cases, theory for the observed solvent isotope effects illuminates the relaxation pathways and mechanisms. Our results suggest several propensity rules for both pathways and mechanisms.     

Vibrational energy transfer in H2 + He

A semiclassical approach is developed to study vibrational energy transfer in H₂ + He by use of the a priori interaction potential including all nonzero impact parameter collisions. The calculated values of the rate coefficient are found to be in excellent agreement with experimental data which are available in the temperature ranges 60–450 K and 1350-3000 K. The temperature dependence is shown to seriously deviate from the Landau-Teller prediction below 1000 K. The calculation was carried out over the temperature range of 30 to 10000 K.     

Vibrational dephasing and energy relaxation of admolecules by phonons

An investigation is made of the vibrational dephasing of a diatomic molecule adsorbed on a surface. Explicit analytic forms for the rate of dephasing by phonons are derived. For comparison, an expression for energy relaxation is given which is appropriate for OH on SiO₂. It is found that the dephasing rate is considerably faster for this system than the energy relaxation rate. These conclusions are compared with the results of a recent experiment.     

Vibrational relaxation of the bending mode of HDO in liquid D2O

The vibrational relaxation of the bending mode of HDO in liquid D2O has been studied using time-resolved mid-infrared pump-probe spectroscopy. At short delays, the transient spectrum clearly shows the v = 1 --> 2 induced absorption and v = 1 --> 0 bleaching and stimulated emission, whereas at long delays, the transient spectrum is dominated by the spectral changes caused by the temperature increase in the sample after vibrational relaxation. From the decay of the v = 1 --> 2 induced absorption, we obtain an estimate of 390 +/- 50 fs for the vibrational lifetime, in surprisingly good agreement with recent theoretical predictions. In the v = 0 --> 1 frequency region, the decay of the absorption change involves a second, slower component, which suggests that after vibrational relaxation the system is not yet in thermal equilibrium.     

Vibrational energy transfer in CH2F2

Infrared fluorescence has been observed from the ν₁, ν₆, 2ν₉, ν₈ and ν₄ levels of CH₂F₂ following excitation by a 9.6 μ Q-switch CO₂ laser. All the observed states exhibit a single exponential decay rate of approximately 44 msec^?1 torr^?1. The rare gas dependence of this rate has also been measured and found to be up to 20 times slower than the rate for the pure gas. Measurements of the risetimes of the observed fluorescence signals yielded an upper limit of 5 μsec at 1 torr for the ν₁, ν₆ and ν₈ levels. The 2ν₉ and ν₄ risetimes were effectively instantaneous under the experimental conditions that prevailed. The relative magnitudes of the measured rate are discussed in terms of existing V-T/R theories and collisional energy transfer processes.     

Vibrational and rotational energy transfer in Ar + HF

State-to-state energy transfer cross sections for Ar + HF (v = 2, 4, and 6; J = 4, 6, 8, and 10) were computed using quasiclassical trajectories. Rotational energy transfer is invariant with increasing v, but vibrational energy transfer is significantly enhanced by increasing J.     

Vibrational energy transfer in hydrogen liquid and its isotopes

The transfer of vibrational energy (V-V) from H₂ to isotopic impurities (HD or D₂) has been studied in the liquid state, between 15 and 30 K. The subsequent relaxation (V-T) of the excited impurity by the H₂ liquid host has also been measured and contrasted with the vibrational relaxation behaviour of pure H₂ and D₂ liquids. The isothermal density dependence of both V-V and V-T transfer has been investigated in the fluid state at 30 K. High density relaxation rates are also compared to our data in the pure gases and to other available gas phase results. Measurements in the solid, near the triple point temperature, are equally reported for each process studied.     

Vibrational dephasing and resonance energy transfer in molecular liquids

The influence of vibrational band-broadening mechanisms (pure dephasing, resonance transfer, depopulation processes) on the vibrational correlation functions of dense fluids is discussed. The coupling between the vibrational and the rotational-translational subsystems is assumed to be weak. It is found that even for weak coupling the homogeneously broadened linewidth (the inverse dephasing time τ^?1) cannot be represented as a sum of widths related to the individual mechanisms. Using an exponential repulsive interaction potential, we obtain numerical estimates for the dephasing time of the 1 ← 0 transition of liquid nitrogen, which agree very well with experimental observations. It turns out that the most significant contribution for τ arises from the weak anharmonicities of the molecular oscillator.     

Vibrational and rotational energy transfer upon molecular collisions

The cross section of the rotational and vibrational energy transfer is derived by using the first Born approximation which quantizes the translational motion of the colliding particles. The theory developed here integrates the intermolecular potential V(R) over all regions of the internuclear distance R by obtaining a Fourier transform of V(R). This differs from previous semiclassical (impact-parameter) treatments which either considered the short-range repulsive interaction or expanded V(R) into a long-range multipole expansion. The cross section obtained here is expressed in a very simple algebraic expression which can be readily calculated. This will be illustrated by examples of CO₂(001)+N₂(υ=0)=CO₂(000)+N₂(υ=1)+18.6 cm^?1 and CO(υ=1)+CO(υ=1)=CO(υ=0)+CO(υ=2)+27 cm^?1. Calculations have been made both for the exothermic and for the endothermic reactions. The comparison of the present results with experimental results as well as with previously calculated results will be discussed.