Highly accurate ab-initio thermochemistry via real-space quantum Monte Carlo: Benzene

TL;DR

This paper demonstrates that real-space quantum Monte Carlo methods can accurately compute the thermochemistry of benzene, achieving near-complete basis set results with favorable computational scaling, outperforming traditional orbital-space methods.

Contribution

It introduces the application of real-space quantum Monte Carlo to thermochemistry, showing its accuracy and scalability for medium-sized molecules like benzene.

Findings

Energies agree with experimental data.

Results comparable to high-accuracy composite methods.

Low computational scaling enables larger system studies.

Abstract

Real-space quantum Monte Carlo is used to calculate the total atomization energy of benzene. In contrast to orbital-space methods common in quantum chemistry, real-space methods allow results at near the complete-basis-set limit to be immediately obtained, all at a computational cost that scales with the fourth power of system size. We demonstrate this utility using the moderately sized benzene molecule, obtaining energies that agree with experiment and previous results from highly accurate composite methods including HEAT and W2. Due to the low scaling of these algorithms, it opens up the possibility of addressing systems out of reach of quantum chemical methods.