The performance of phaseless auxiliary-field quantum Monte Carlo on the ground state electronic energy of benzene.

Abstract

The ground state electronic energy of benzene is the focus of a recent blind test by Eriksen and co-workers [arXiv:2008.02678]. In this note, we report the phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) results on the identical problem. We examine trial wavefunctions of the spin-restricted Hartree-Fock (RHF), and complete active space self-consistent field (CASSCF) with an active space of 6-electron and 6-orbital (i.e., CAS(6,6)) form for the cc-pVDZ basis set. ph-AFQMC+RHF deviates from the value where many methods agreed on (i.e., -863 m$E_h$) by -3.1(3) m$E_h$ whereas ph-AFQMC+CAS(6,6) deviates from the same value by -1.3(4) m$E_h$. In addition to this, we report the frozen core correlation energy of ph-AFQMC+RHF in the cc-pVTZ and cc-pVQZ basis sets as well as their complete basis set limit. Our findings highlight the accuracy, flexibility, and scalability of ph-AFQMC with simple trial wavefunctions.