Influence of vibrational cooling on the time-dependence of stokes and anti-stokes resonance raman scattering

The kinetics of Stokes and anti-Stokes resonance Raman intensities of TINUVIN observed after a completed proton transfer cycle is reported. This kinetics of the strongly vibrationally excited molecules can not be described in terms of population numbers of the vibrations alone but demands for considering the influence of time-dependent line shape functions. Based on transform theory, we calculated the dynamics of these functions and corresponding resonance Raman kinetics from the temperature-dependent electronic absorption bands. Using a simple model, these calculations reproduce main characteristics of the measured resonance Raman kinetics. Our results demonstrate how dramatically the time-dependence of the line shape function influences the Stokes as well as the anti-Stokes resonance Raman kinetics of highly vibrationally excited molecules. q 2004 Elsevier B.V. All rights reserved