A phaseless auxiliary-field quantum Monte Carlo perspective on the uniform electron gas at finite temperatures: Issues, observations, and benchmark study.

ABSTRACT

We investigate the viability of the phaseless finite-temperature auxiliary-field quantum Monte Carlo (ph-FT-AFQMC) method for ab initio systems using the uniform electron gas as a model. Through comparisons with exact results and FT coupled cluster theory, we find that ph-FT-AFQMC is sufficiently accurate at high to intermediate electronic densities. We show, both analytically and numerically, that the phaseless constraint at FT is fundamentally different from its zero-temperature counterpart (i.e., ph-ZT-AFQMC), and generally, one should not expect ph-FT-AFQMC to agree with ph-ZT-AFQMC in the low-temperature limit. With an efficient implementation, we are able to compare exchange-correlation energies to the existing results in the thermodynamic limit and find that the existing parameterizations are highly accurate. In particular, we found that ph-FT-AFQMC exchange-correlation energies are in better agreement with a known parameterization than is restricted path-integral MC in the regime of Θ ≤ 0.5 and rs ≤ 2, which highlights the strength of ph-FT-AFQMC.