Self-consistent field theory based molecular dynamics with linear system-size scaling

TL;DR

This paper introduces a novel linear scaling molecular dynamics method based on self-consistent field theory that enables accurate all-electron calculations for metals and addresses energy drift issues in simulations.

Contribution

It presents an improved, exact decomposition of the grand canonical potential that does not require orbital localization or well-conditioned Hamiltonians, enhancing accuracy and applicability.

Findings

Enables highly accurate all-electron calculations for metallic systems.

Circumvents energy drift in molecular dynamics via a modified Langevin equation.

Demonstrates effectiveness with liquid methane under extreme conditions.

Abstract

We present an improved field-theoretic approach to the grand-canonical potential suitable for linear scaling molecular dynamics simulations using forces from self-consistent electronic structure calculations. It is based on an exact decomposition of the grand canonical potential for independent fermions and does neither rely on the ability to localize the orbitals nor that the Hamilton operator is well-conditioned. Hence, this scheme enables highly accurate all-electron linear scaling calculations even for metallic systems. The inherent energy drift of Born-Oppenheimer molecular dynamics simulations, arising from an incomplete convergence of the self-consistent field cycle, is circumvented by means of a properly modified Langevin equation. The predictive power of the present linear scaling \textit{ab-initio} molecular dynamics approach is illustrated using the example of liquid methane under extreme conditions.