Accurate nonadiabatic quantum dynamics on the cheap: making the most of mean field theory with master equations.
In this article, we show how Ehrenfest mean field theory can be made both a more accurate and efficient method to treat nonadiabatic quantum dynamics by combining it with the generalized quantum master equation framework. The resulting mean field generalized quantum master equation (MF-GQME) approach is a non-perturbative and non-Markovian theory to treat open quantum systems without any restrictions on the form of the Hamiltonian that it can be applied to. By studying relaxation dynamics in a wide range of dynamical regimes, typical of charge and energy transfer, we show that MF-GQME provides a much higher accuracy than a direct application of mean field theory. In addition, these increases in accuracy are accompanied by computational speed-ups of between one and two orders of magnitude that become larger as the system becomes more nonadiabatic. This combination of quantum-classical theory and master equation techniques thus makes it possible to obtain the accuracy of much more computationally expensive approaches at a cost lower than even mean field dynamics, providing the ability to treat the quantum dynamics of atomistic condensed phase systems for long times.
Department of Chemistry, Stanford University, Stanford, California 94305, USA.
Aaron
A
Kelly
Department of Physics, Stanford University, Stanford, California 94305, USA.
Nora
N
Brackbill
Department of Chemistry, Stanford University, Stanford, California 94305, USA.
Thomas E
TE
Markland