Benchmarking Quasiclassical Mapping Hamiltonian Methods for Simulating Electronically Nonadiabatic Molecular Dynamics

Quasi-classical mapping Hamiltonian methods have recently emerged as a promising approach for simulating electronically nonadiabatic molecular dynamics. The classical-like dynamics of the overall system within these methods makes them computationally feasible, and they can be derived based on well-defined semiclassical approximations. However, the existence of a variety of different quasi-classical mapping Hamiltonian methods necessitates a systematic comparison of their respective advantages and limitations. Such a benchmark comparison is presented in this paper. The approaches compared include the Ehrenfest method, the symmetrical quasi-classical (SQC) method, and five variations of the linearized semiclassical (LSC) method, three of which employ a modified identity operator. The comparison is based on a number of popular nonadiabatic model systems; the spin-boson model, a Frenkel biexciton model, and Tully’s scattering models 1 and 2. The relative accuracy of the different methods is tested by comparing with quantum-mechanically exact results for the dynamics of the electronic populations and coherences. We find that LSC with the modified identity operator typically performs better than the Ehrenfest and standard LSC approaches. In comparison to SQC, these modified methods appear to be slightly more accurate for condensed phase problems, but for scattering models there is little distinction between them.
Journal of Chemical Theory and Computation, 16 (5)
ISSN:1549-9618
ISSN:1549-9626