Nonadiabatic Quantum Molecular Dynamics in Dense Manifolds of Electronic States.

Abstract

Most nonadiabatic molecular dynamics methods require the determination of a basis of adiabatic or diabatic electronic states at every time step, but in dense manifolds of electronic states, such approaches become intractable. A notable exception is Ehrenfest molecular dynamics, which can be implemented without explicit determination of such a basis but suffers from unphysical behavior when propagation on a mean-field potential energy surface (PES) does not accurately reflect the true dynamics on multiple electronic states. Here we introduce the multiple cloning for dense manifolds of states (MCDMS) method, a systematically improvable approximation to the multiple cloning method. MCDMS avoids both the mean-field PES problem and the need to compute the full electronic spectrum. This is achieved by reformulating multiple cloning to use a subspace of approximate eigenstates constructed from the time-dependent Ehrenfest electronic wave function. By application to model systems, we show that this approach allows a substantial reduction in the size of the required electronic basis without significant loss in accuracy.