Quantum-mechanical evaluation of the Boltzmann operator in correlation functions for large molecular systems: a multilayer multiconfiguration time-dependent Hartree approach.
It is shown that the Boltzmann operator in time correlation functions for complex molecular systems can be evaluated in a numerically exact way employing the multilayer formulation of the multiconfiguration time-dependent Hartree theory in combination with Monte Carlo importance sampling techniques. The performance of the method is illustrated by selected applications to photoinduced intervalence electron transfer reactions in the condensed phase. Furthermore, the validity of approximate schemes to evaluate the Boltzmann is discussed.
Wang
Haobin
H
Department of Chemistry and Biochemistry, MSC 3C, New Mexico State University, Las Cruces, New Mexico 88003, USA. whb@intrepid.nmsu.edu
Thoss
Michael
M