Path-ordered linked product approximation to the global electronic overlap matrix

TL;DR

This paper introduces a path-ordered product approximation for the electronic overlap matrix, significantly reducing computational costs while accurately capturing conical intersection dynamics in nonadiabatic wave packet simulations.

Contribution

The authors propose a novel approximation method for the electronic overlap matrix using a product of nearest-neighbor overlaps, enabling efficient and accurate nonadiabatic dynamics modeling.

Findings

Approximate overlap matrix closely reproduces exact conical intersection dynamics.

Method reduces computational effort by avoiding full electronic structure calculations.

Demonstrated effectiveness on a proton-coupled electron transfer model.

Abstract

The global many-electron wave function overlap matrix accounts for all effects beyond the Born-Oppenheimer approximation in the discrete variable local diabatic representation, a numerically exact framework for modeling nonadiabatic conical intersection wave packet dynamics. Nevertheless, calculating the electronic overlap matrix from electronic structure is computationally expensive. Here, we introduce an approximation for constructing the electronic overlap matrix between any two long-range geometries by the product of nearest-neighbor overlap matrices along a path connecting these two geometries. This approximation significantly reduces the computational effort by only requiring electronic structure calculations for the nearest-neighbor overlap matrices. The accuracy of this approximation is demonstrated through an exact simulation of a proton-coupled electron transfer model. Our results show that although the approximate overlap matrix can exhibit noticeable differences from the exact ones, the conical intersection dynamics is in almost exact agreement with those from the exact overlap matrix.