Vibrational relaxation and Bloch-Redfield theory

Bloch–Redfield theory helps bridge the gap between classical molecular dynamics (MD) simulations and (still unavailable) full quantum-mechanical simulation of processes in condensed media. It allows one to describe quantum processes in terms of a few parameters which can be computed from MD simulations. In this letter we present results which show that it is practical to use Bloch–Redfield theory to describe the relaxation of high-energy (≥kT) vibrational modes and that it gives answers which differ from the classical MD ones.