Fully analytic G$_0$W$_0$ nuclear gradients

TL;DR

This paper introduces the first fully analytic nuclear gradients for the G$_0$W$_0$ method, enabling more efficient and accurate calculations of molecular properties by leveraging a connection to coupled-cluster theory.

Contribution

It provides the first analytic derivation and implementation of G$_0$W$_0$ nuclear gradients, validated against finite differences and compared with other methods and experimental data.

Findings

Validated analytic gradients against finite differences.

Examined the Tamm--Dancoff approximation's effect on results.

Compared G$_0$W$_0$ ionization potentials and electron affinities with other methods and experiments.

Abstract

In this letter, we present the first fully analytic derivation and implementation of nuclear gradients for the G$_0$W$_0$ method. For this, we leverage the recently established connection between the G$_0$W$_0$ approach and equation-of-motion unitary coupled-cluster theory for charged excitations [J. Chem. Phys. 158, 124123 (2023)]. Analytic gradients are obtained through the Lagrangian technique and are implemented and validated by comparison with finite-difference calculations. For G$_0$W$_0$, we examine the effect of the Tamm--Dancoff approximation for evaluating the screened Coulomb interaction. Finally, we compare G$_0$W$_0$ adiabatic ionization potential and electron affinities to wavefunction-based electronic structure methods, and experimental values.