Molecular dynamics with time dependent quantum Monte Carlo

TL;DR

This paper introduces a novel ab initio quantum molecular dynamics method that models both electrons and nuclei quantum mechanically or semi-classically, capturing quantum correlations and applied to hydrogen molecules under ultrashort laser pulses.

Contribution

It develops a new approach combining quantum trajectories and guiding waves for molecular dynamics, incorporating quantum correlations in a self-consistent framework.

Findings

Accurately models hydrogen molecule ionization under ultrashort pulses.

Captures quantum correlation effects beyond classical approximations.

Shows good agreement with exact Ehrenfest dynamics results.

Abstract

In this paper we propose an ab initio method to solve quantum many-body problems of molecular dynamics where both the electronic and the nuclear degrees are represented by ensembles of trajectories and guiding waves in physical space. Both electrons and nuclei can be treated quantum mechanically where the guiding waves obey a set of coupled Schrodinger equations (quantum-quantum description) or, alternatively, coupled Schroedinger-Newtonian equations are solved for the quantum-classical approximation. The method takes into account local and non-local quantum correlation effects in a self consistent manner. The general formalism is applied to one- and two-dimensional hydrogen molecule subjected to a strong ultashort optical pulse. Comparison is made with the results from the 'exact' Ehrenfest molecular dynamics for the molecular ionization and for the evolution of the inter-nuclear distance as the molecule dissociates.