Analytic $G_0W_0$ gradients based on a double-similarity transformation equation-of-motion coupled-cluster treatment

TL;DR

This paper introduces an analytic method for calculating $G_0W_0$ nuclear gradients using a modified equation-of-motion coupled-cluster approach, improving the accuracy of ionization potential predictions.

Contribution

It develops a new fully analytic $G_0W_0$ gradient formulation based on a double-similarity transformation within the equation-of-motion coupled-cluster framework.

Findings

Enables accurate computation of ionization potential gradients.

Provides a more complete correlation treatment in $GW$ calculations.

Facilitates studies of molecular reactivity and spectroscopic properties.

Abstract

The accurate prediction of ionization potentials (IPs) is central to understanding molecular reactivity, redox behavior, and spectroscopic properties. While vertical IPs can be accessed directly from electronic excitations at fixed nuclear geometries, the computation of adiabatic IPs requires nuclear gradients of the ionized states, posing a major theoretical and computational challenge, especially within correlated frameworks. Among the most promising approaches for IP calculations is the many-body Green's function $GW$ method, which provides a balanced compromise between accuracy and computational efficiency. Furthermore, it is applicable to both finite and extended systems. Recent work has established formal connections between $GW$ and coupled-cluster doubles (CCD) theory, leading to the first derivation of analytic $GW$ nuclear gradients via a unitary CCD framework. In this work, we present an alternative, fully analytic formulation of $GW$ nuclear gradients based on a modified version of the traditional equation-of-motion CCD formalism, enabling the inclusion of missing correlation effects in the traditional CCD methods.