Benchmarking Quasiclassical Mapping Hamiltonian Methods for Simulating Electronically Nonadiabatic Molecular Dynamics

Abstract

Quasi-classical mapping Hamiltonian methods have recently emerged as a promising approach for simulating electronically nonadiabatic molecular dynamics. The classicallike 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 bi-exciton model and 1

A molecular perspective on Tully models for nonadiabatic dynamics

“…Phys., 2020, 22, 15183--15196 | 15185 matrix dynamics, 40 ring polymer surface hopping, 41 quantum trajectory surface hopping, 42 consensus surface hopping, 43 or quasiclassical mapping Hamiltonian methods. 44 The Tully models were also used to assess decoherence in nonadiabatic dynamics or to test newly-developed decoherence corrections for the TSH, see ref. [45][46][47][48][49][50][51][52] for examples.…”

Non-adiabatic Matsubara Dynamics and Non-adiabatic Ring Polymer Molecular Dynamics

“…The numerical comparison between these two approaches has been extensively discussed in the recent work, 109,112,113 and the recent development on choosing the identity operator 109,113,114 has also shown to significantly improve the population dynamics, even just using a less accurate Liouvillian L [1] LSC . Along the same direction, one can use the mapping action variable's Wigner transform 115 to construct [Â] W and [B] W , and engineer various shapes of Window functions for these estimators.…”

On-the-fly Symmetrical Quasi-classical Dynamics with Meyer-Miller Mapping Hamiltonian for the Treatment of Nonadiabatic Dynamics at Conical Intersections

“…38,[73][74][75][76][77][78][79][80][81][82][83][84][85][86][87][88][89][90] The reasonable performance of the SQC/MM dynamics was examined by different benchmark works. 47,[81][82][86][87]89 Within the framework of the SQC/MM dynamics, Cotton and Miller suggested different useful approaches in the implementation, such as the triangle windowing technique 80,91 and the employment of the trajectory-adjusted electronic ZPE correction 92 in the SQC/MM approach. The SQC/MM method was employed to treat different types of nonadiabatic dynamics, 38,73,[81][82][83][84][85][86]93 for example excited-state energy/electronic transfer dynamics, 73,81,86,90,93 singlet fission [83][84][85] and scattering dynamics 82 and photo-dissociation dynamics.…”