Kinetics of thermal excitation of a molecule in a condensed medium

Abstract

A microscopic model for thermal excitation of vibrational ground state of a molecule interacting with a condensed medium is developed. The master equation for evolution of occupancies of the vibrational levels is derived. The rate constant limiting the process of molecular thermal excitation is determined analytically. It is shown that while this quantity is independent of temperature at low temperatures coinciding with a rate speed limit for quantum transitions due to uncertainty principle, at high temperatures it rather linearly rises with temperature according to the Einstein's relation for adiabatic transitions.