Time dependent density functional theory for nonadiabatic electronic dynamics

TL;DR

This paper develops a formalism for exact time-dependent density functional theory applicable to nonadiabatic electronic dynamics, enabling rigorous simulations of interacting electron-nuclear systems.

Contribution

It introduces a formalism that allows exact reproduction of the density matrix of interacting systems using noninteracting reference systems, extending TDDFT to nonadiabatic regimes.

Findings

Formalism reproduces the density matrix exactly

Runge-Gross and Van Leeuwen theorems are special cases

Enables rigorous nonadiabatic electronic dynamics simulations

Abstract

We show that the time dependent single electron, nuclear density matrix of an interacting electronic system coupled to nuclear degrees of freedom can be exactly reproduced by that of an electronic system with arbitrarily specified electron-electron interactions coupled to the same nuclear degrees of freedom, given the initial density matrix of the interacting system. This formalism enables the construction of rigorous time dependent density functional theories to study nonadiabatic electronic dynamics. We obtain the Runge-Gross and Van Leeuwen theorems as special cases in the adiabatic limit.