Appraisal of Surface Hopping as a Tool for Modeling Condensed Phase Linear Absorption Spectra

Abstract

Whereas surface hopping is usually used to study populations and mean-field dynamics to study coherences, in two recent papers, we described a procedure for calculating dipole−dipole correlation functions (and therefore absorption spectra) directly from ensembles of surface hopping trajectories. We previously applied this method to a handful of one-dimensional model problems intended to mimic the gas phase. In this article, we now benchmark this new procedure on a set of multidimensional model problems intended to mimic the condensed phase and compare our results against other standard semiclassical methods. By comparison, we demonstrate that methods that include only dynamical information from one PES (the standard Kubo approaches) exhibit large discrepancies with the results of exact quantum dynamics. Furthermore, for model problems with nonadiabatic excited state dynamics but no quantized vibrational structure in the spectra, our surface hopping approach performs comparably to using Ehrenfest dynamics to calculate the electronic coherences. That being said, however, when quantized vibrational structures are present in the spectra but the electronic states are uncoupled, performing the dynamics on the mean PES still outperforms our present method. These benchmark results should influence future studies that use ensembles of independent semiclassical trajectories to model linear as well as multidimensional spectra in the condensed phase.

Effects of different initial condition samplings on photodynamics and spectrum of pyrrole

“…(This and more involved approaches for spectrum simulations are discussed, for instance, in Ref. .) The nuclear ensemble approach is also very handy as the initial step for excited‐state dynamics simulations.…”

Equilibrium Fermi’s Golden Rule Charge Transfer Rate Constants in the Condensed Phase: The Linearized Semiclassical Method vs Classical Marcus Theory

“…(6) corresponds to electronic dephasing is also the main reason for why predictions based on methods like fewest-switches surfacehopping, [20][21][22]59,60 Ehrenfest dynamics, 20 and ring-polymer molecular dynamics 19 …”

A surface-hopping method for semiclassical calculations of cross sections for radiative association with electronic transitions

“…The surface-hopping methodology allows the study of radiative association with electronic transitions to be extended to arbitrary polyatomic system. The surface-hopping method is widely used in the modeling of nonadiabatic molecular processes [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] . The idea of this method originally put forward by Bjerre and Nikitin 48 and later advanced by others [49][50][51][52][53] .…”

“…The surface-hopping method is widely used in the modeling of nonadiabatic molecular processes [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47] . The idea of this method originally put forward by Bjerre and Nikitin 48 and later advanced by others [49][50][51][52][53] .…”