Short-time Accuracy and Intra-electron Correlation for Nonadiabatic Quantum-Classical Mapping Approaches

Abstract

Nonadiabatic quantum-classical mapping approaches have significantly gained in popularity in the past several decades because they have acceptable accuracy while remaining numerically tractable even for large system sizes. In the recent few years, several novel mapping approaches have been developed that display higher accuracy than the traditional Ehrenfest method, linearized semiclassical initial value representation (LSC-IVR), and Poisson bracket mapping equation (PBME) approaches. While various benchmarks have already demonstrated the advantages and limitations of those methods, rigorous theoretical justifications of their short-time accuracy are still demanded. In this article, we systematically examine the intra-electron correlation, as a statistical measure of electronic phase space, which has been first formally proposed for mapping approaches in the context of the generalized discrete truncated Wigner approximation (GDTWA) and which is a key ingredient for the improvement of short-time accuracy of such mapping approaches. We rigorously establish the connection between short-time accuracy and intra-electron correlation for various widely used models. We find that LSC-IVR, PBME, and Ehrenfest methods fail to correctly reproduce the intra-electron correlation. While some of the traceless Meyer--Miller--Stock--Thoss (MMST) approaches, partially linearized density matrix (PLDM) approach, and spin partially linearized density matrix (Spin-PLDM) approach are able to sample the intra-electron correlation correctly, the spin linearized semiclassical (Spin-LSC) approach and the other traceless MMST approaches sample the intra-correlation faithfully only for two-level systems. Our theoretical analysis provides insights into the short-time accuracy of semiclassical methods and presents mathematical justifications for previous numerical benchmarks.