Improving the Accuracy of Quasiclassical Mapping Hamiltonian Methods by Treating the Window Function Width as an Adjustable Parameter.

Mapping Hamiltonian methods for simulating electronically nonadiabatic molecular dynamics are based on representing the electronic population and coherence operators in terms of isomorphic mapping operators, which are given in terms of the auxiliary position and momentum operators. Adding a quasiclassical approximation then makes it possible to treat those auxiliary coordinates and momenta, as well as the nuclear coordinates and momenta, as classical-like phase-space variables. Within such quasiclassical mapping Hamiltonian methods, the initial sampling of the auxiliary coordinates and momenta and the calculation of expectation values of electronic observables at a later time are based on window functions whose functional form differ from one method to another. However, different methods also differ with respect to the way in which they treat the window width. More specifically, while the window width is treated as an adjustable parameter within the symmetrical quasiclassical (SQC) method, this has not been the case for methods based on the linearized semiclasscial (LSC) approximation. In the present study, we investigate the effect that turning the window width into an adjustable parameter within LSC-based methods has on their accuracy compared to SQC. The analysis is performed in the context of the spin-boson and Fenna-Matthews-Olson (FMO) complex benchmark models. We find that treating the window width in LSC-based methods as an adjustable parameter can make their accuracy comparable to that of the SQC method.