Ab-Initio Molecular Dynamics with Screened Lorentz Forces. Part I. Calculation and Atomic Charge Interpretation of Berry Curvature

TL;DR

This paper introduces a numerical scheme to calculate Berry curvature in molecules under magnetic fields, enabling more accurate ab initio molecular dynamics simulations by accounting for screening Lorentz forces.

Contribution

It presents a finite-difference method for Berry curvature calculation, addressing phase challenges, and demonstrates its application to molecules using London orbitals for gauge invariance.

Findings

Berry curvature varies with bond distance and magnetic field strength.

The method ensures gauge-origin invariance using London orbitals.

Berry curvature can be interpreted through atomic charges.

Abstract

The dynamics of a molecule in a magnetic field is significantly different form its zero-field counterpart. One important difference in the presence of a field is the Lorentz force acting on the nuclei, which can be decomposed as the sum of the bare nuclear Lorentz force and a screening force due to the electrons. This screening force is calculated from the Berry curvature and can change the dynamics qualitatively. It is therefore important to include the contributions from the Berry curvature in molecular dynamics simulations in a magnetic field. In this work, we present a scheme for calculating the Berry curvature numerically, by a finite-difference technique, addressing challenges related to the arbitrary global phase of the wave function. The Berry curvature is calculated as a function of bond distance for H$_2$ at the restricted and unrestricted Hartree--Fock levels of theory and for CH$^{+}$ as a function of the magnetic field strength at the restricted Hartree--Fock level of theory. The calculations are carried out using basis sets of contracted Gaussian functions equipped with London phase factors (London orbitals) to ensure gauge-origin invariance. In the paper, we also interpret the Berry curvature in terms of atomic charges and discuss its convergence in basis sets with and without London phase factors. Calculation of the Berry curvature allows for its inclusion in \textit{ab initio} molecular dynamics simulations in a magnetic field.