Analytical gradients of random-phase approximation plus corrections from renormalized single excitations

TL;DR

This paper develops and implements the first analytical gradient method for RPA plus renormalized single excitation (rSE) corrections, enabling accurate molecular geometry optimizations and energy calculations within this advanced quantum chemistry framework.

Contribution

It introduces the first analytical gradient formulation for RPA+rSE energies, allowing for structural relaxations and improved energetics predictions.

Findings

RPA+rSE corrects RPA's overestimation for dispersion-bound molecules.

The approach accurately predicts water cluster geometries.

RPA+rSE reduces mean absolute energy errors in benchmark tests.

Abstract

The random-phase approximation (RPA) formulated within the adiabatic connection fluctuation-dissipation framework is a powerful approach to compute the ground-state energies and properties of molecules and materials. Its overall underbinding behavior can be effectively mitigated by a simple correction term, called renormalized single excitation (rSE) correction. Analytical gradient calculations of the RPA energy have become increasingly available, enabling structural relaxations and even molecular dynamics at the RPA level. However, such calculations at the RPA+rSE level have not been reported, due to the lack of the rSE analytical gradient. Here, we present the first formulation and implementation of the analytical gradients of the rSE energy with respect to the nuclear coordinates within an atomic-orbital basis set framework, which allows us to assess the performance of RPA+rSE in determining the molecular geometries and energetics. It is found that the slight overestimation behavior of RPA for small covalently bonded molecules is strengthened by rSE, while such behavior for molecules bonded with purely dispersion interactions is corrected. We further applied the approach to the water clusters, and found that the energy difference between the low-energy isomers of water hexamers is almost unchanged when going from RPA to RPA+rSE geometries. For the bigger WATER27 test set, using the RPA+rSE geometries instead of the RPA ones leads to a slight reduction of the mean absolute error of RPA+rSE from 0.91 kcal/mol to 0.70 kcal/mol, at the complete basis set.