Selecting Optimal Unrestricted Hartree–Fock Trial Wave Functions for Phaseless Auxiliary-Field Quantum Monte Carlo: Accuracy and Limitations in Modeling Three Iron–Sulfur Clusters

Abstract

Phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC) has emerged as a promising electronic structure method for correlated electronic systems. However, the quality of its predictions depends critically on the choice of trial wave function, and it is not obvious how to make an optimal choice, especially for strongly correlated states of large systems. Mean-field wave functions are compelling trial wave function candidates, as they map directly to chemical concepts and can be obtained withO(N4) cost. Yet in the strongly correlated regime, one faces a symmetry dilemma and the existence of multiple nearly degenerate solutions. In this work, we investigate active space models of [2Fe–2S]2+, mixed-valent [4Fe–4S]2+, and [4Fe–4S]4+ and explore the sensitivity of ph-AFQMC to the choice of unrestricted Hartree–Fock trial wave function. We find that surprisingly accurate ground-state energies for these systems can be obtained when trial selection is guided by chemical properties and physical symmetries, rather than the variational energy. However, in all cases, we find a rapidly decaying overlap between the stochastic wave function and the UHF trial, indicating that the trials are acting as suboptimal importance functions. By analogy to a similar situation in the stretched helium dimer cation, we show how this sampling bias pushes ph-AFQMC with UHF trials toward artificially negative energies, which evidently can be compensated for by the phaseless bias in certain cases.