Vibrational energy relaxation of polyatomic molecules in liquids: The solvent’s perspective

Abstract

Articles you may be interested inAn analysis of molecular origin of vibrational energy transfer from solute to solvent based upon path integral influence functional theory Vibrational energy relaxation of azulene in the S 2 state. I. Solvent species dependence Molecular dynamics simulation of vibrational energy relaxation of highly excited molecules in fluids. III. Equilibrium simulations of vibrational energy relaxation of azulene in carbon dioxide J. Chem. Phys. 111, 8022 (1999); 10.1063/1.480135 Molecular dynamics simulation of vibrational relaxation of highly excited molecules in fluids. II. Nonequilibrium simulation of azulene in CO 2 and Xe J. Chem. Phys. 110, 5286 (1999); 10.1063/1.478423 Vibrational relaxation of azide ion in water: The role of intramolecular charge fluctuation and solvent-induced vibrational coupling

Effects of friction and asymmetric inner sphere reorganization energy on the electron transfer reaction rate—Two-dimensional simulations

“…Similar conclusions were derived from the experimental measurement [42]. The problem of the vibrational and rotational friction were also addressed in extensive studies performed by the group of Stratt [43][44][45][46][47][48]. An interesting review of general concepts proposed in the literature and related to the dynamical solvent effects on the electron transfer reactions, which are the subject of our work, was given by Weaver [49].…”

“…The group of Stratt [43][44][45][46][47][48] used the instantaneous normal modes (INM) analysis of vibrational friction to explore the frequency dependent friction exerted on a single particle as well as diatomic and three atomic molecules. Their results show how difficult and complex is this problem.…”

Vibrational relaxation of CH3I in the gas phase and in solution

“…2-5 Line broadening frequently makes linear spectroscopy impractical in solution, however, and time-domain methods are generally a better approach. 8,24 Pump-probe experiments directly observe energy flow within and out of a molecule by exciting a nonstationary vibrational state with one laser pulse and then probing the evolution of the system as a function of time with a second pulse. 25,26 Infrared absorption, [27][28][29][30][31][32] anti-Stokes Raman scattering, [33][34][35][36][37] and ultraviolet absorption [38][39][40][41][42][43][44][45][46][47][48][49] are the most common methods for probing the vibrational dynamics in the ground electronic state and are generally most useful in the condensed phase where it is possible to obtain a high density of vibrationally excited molecules.…”

Uncovering molecular relaxation processes with nonlinear spectroscopies in the deep UV

“…With respect to mechanism (i), it is generally thought that vibrational energy is most effectively accepted by modes of the solvent with frequencies less than 300 cm À1 because they are associated with the greatest ''friction'' [93,94]. In contrast, mechanism (ii) involves a cascade of transitions in which the overall rate is governed by the ability of the solute to concentrate energy in its lowest frequency intramolecular vibrations [94,95]. This picture, wherein the low frequency modes of the solvent are the primary energy acceptors, is challenged by the observation of pronounced isotope effects (e.g., deuteration of water) on the rate of VET in hydrogen-bonding solvents [96,97].…”