Fully Analytic Nuclear Gradients for the Bethe--Salpeter Equation

TL;DR

This paper introduces the first fully analytic nuclear gradients for the Bethe-Salpeter equation combined with the G0W0 approximation, enabling efficient and accurate excited-state calculations in molecules.

Contribution

It derives and implements analytic nuclear gradients for BSE@G0W0, advancing computational methods for molecular excited states.

Findings

Validated implementation against numerical gradients.

Compared excited-state geometries with wavefunction methods.

Demonstrated efficiency of the analytic gradients.

Abstract

The Bethe-Salpeter equation (BSE) formalism, combined with the $GW$ approximation for ionization energies and electron affinities, is emerging as an efficient and accurate method for predicting optical excitations in molecules. In this letter, we present the first derivation and implementation of fully analytic nuclear gradients for the BSE@$G_0W_0$ method. Building on recent developments for $G_0W_0$ nuclear gradients, we derive analytic nuclear gradients for several BSE@$G_0W_0$ variants. We validate our implementation against numerical gradients and compare excited-state geometries and adiabatic excitation energies obtained from different BSE@$G_0W_0$ variants with those from state-of-the-art wavefunction methods.