Phaseless auxiliary-field quantum Monte Carlo method for cavity-QED matter systems

TL;DR

This paper introduces a generalized phaseless auxiliary-field quantum Monte Carlo method tailored for cavity QED matter systems, demonstrating high accuracy and scalability for simulating light-matter interactions in molecules and extended systems.

Contribution

The authors develop a versatile AFQMC approach applicable in Coulomb and dipole gauges, improving accuracy and enabling broader QED matter system simulations.

Findings

Gauge invariance achieved within Gaussian basis sets

QED-CCSD accuracy improved with perturbative triples correction

Efficient evaluation of photon occupation number in any gauge

Abstract

We present a generalization of the phaseless auxiliary-field quantum Monte Carlo (AFQMC) method to cavity quantum-electrodynamical (QED) matter systems. The method can be formulated in both the Coulomb and the dipole gauge. We verify its accuracy by benchmarking calculations on a set of small molecules against full configuration interaction and state-of-the-art QED coupled cluster (QED-CCSD) calculations. Our results show that (i) gauge invariance can be achieved within correlation-consistent Gaussian basis sets, (ii) the accuracy of QED-CCSD can be enhanced significantly by adding the standard perturbative triples correction without light-matter coupling, and (iii) there is a straightforward way to evaluate the differential expression for the photon occupation number that works in any gauge. The high accuracy and favorable computational scaling of our AFQMC approach will enable a broad range of applications. Besides polaritonic chemistry, the method opens a way to simulate extended QED matter systems.