Vibrational Relaxation Description In the Coherent Domain and Inverted Temperature Dependence of Relaxation Rates

The vibrational relaxation of molecules embedded in an environment is described in terms of a generalized master equation that is based on, but goes beyond, the well-known Montroll-Shuler equation$^1$ in chemical physics. Relaxation rates are calculated explicitly on the basis of our theory$^2$ for given microscopic Hamiltonians representing the molecule-bath interaction and the problem of “inverted temperature dependence” reported$^3$ in some observations is addressed. $[1]$ E. W. Montroll and K. E. Shuler, J. Chem. Phys. (1957). $[2]$ V. M. Kenkre and M. Chase. Preprint. $[3]$ A. Tokmakoff, B. Sauter, and M. D. Fayer. J. Chem. Phys. (1994).