Resonating Valence Bond Quantum Monte Carlo: Application to the ozone molecule

TL;DR

This paper applies a resonating valence bond quantum Monte Carlo method to accurately compute the ozone molecule's potential energy surface, capturing static and dynamic electron correlations in strongly correlated systems.

Contribution

It introduces a wave function combining antisymmetrized geminal power and Jastrow factors for improved quantum Monte Carlo simulations of molecules.

Findings

Accurately describes ozone's potential energy surface in multiple vibrational states.

Quantitative agreement with experimental data.

Effectively captures static and dynamic electron correlations.

Abstract

We study the potential energy surface of the ozone molecule by means of Quantum Monte Carlo simulations based on the resonating valence bond concept. The trial wave function consists of an antisymmetrized geminal power arranged in a single-determinant that is multiplied by a Jastrow correlation factor. Whereas the determinantal part incorporates static correlation effects, the augmented real-space correlation factor accounts for the dynamics electron correlation. The accuracy of this approach is demonstrated by computing the potential energy surface for the ozone molecule in three vibrational states: symmetric, asymmetric and scissoring. We find that the employed wave function provides a detailed description of rather strongly-correlated multi-reference systems, which is in quantitative agreement with experiment.