Open-shell Configuration State Functions as trial states for phaseless auxiliary-field quantum Monte Carlo

Abstract

The accurate description of open-shell states in molecular systems poses challenges for approximate electronic structure methods. One emerging approach is to variationally optimize the orbitals of a single user-selected Configuration State Function (CSF), i.e., a linear combination of Slater determinants that is constructed as an eigenstate of the total spin operator. In this work we explore the use of these orbital-optimized single CSFs as trial wavefunctions in phaseless auxiliary-field quantum Monte Carlo (ph-AFQMC), a stochastic method that recovers electron correlation by evolving an initial state in imaginary time, subject to a constraint imposed by the trial state. We investigate the symmetric stretch of H-He-H, a series of small $p$-block compounds with diradicaloid singlet states, twisted ethene conformers, and a bimetallic iron-sulfur complex. We find that accurate energetics are obtained for states dominated by open-shell character, and that for certain atoms and diatomics the accuracy can be significantly improved when the trial is made to also preserve the relevant angular momentum symmetries. Furthermore, our study reveals that the open-shell CSF trial is suboptimal when the target electronic state reflects a significant mixture of ionic and covalent character, e.g., at shorter bond lengths in H-He-H and for the superexchange-stabilized ground state of [2Fe-2S]$^{2+}$. Our findings suggest that ph-AFQMC using CSF trial states is a promising method for many (but not all) strongly correlated molecular states, especially given its relatively low computational cost, and that it provides a reasonable non-perturbative way to recover some of the dynamic correlation that is otherwise missing in the CSF.