Simulations of photoinduced processes with the exact factorization: State of the art and perspectives

Abstract

This Perspective offers an overview on the applications of the exact factorization of the electron-nuclear wavefunction to the domain of theoretical photochemistry, where the aim is to gain insights into the ultrafast dynamics of molecular systems via simulations of their excited-state dynamics beyond the Born-Oppenheimer approximation. The exact factorization offers an alternative viewpoint to the Born-Huang representation for the interpretation of dynamical processes involving the electronic ground and excited states as well as their nonadiabatic coupling through the nuclear motion. Therefore, the formalism has been used to derive algorithms for quantum molecular-dynamics simulations where the nuclear motion is treated using trajectories and the electrons are treated quantum mechanically. These algorithms have the characteristic features of being based on coupled and on auxiliary trajectories, and have shown excellent performance in describing a variety of excited-state processes, as this Perspective illustrates. We conclude with a discussion on the authors’ point of view on the future of the exact factorization.