Spectral Functions from Auxiliary-Field Quantum Monte Carlo without Analytic Continuation: The Extended Koopmans' Theorem Approach.

Abstract

We explore the extended Koopmans' theorem (EKT) within the phaseless auxiliary-field quantum Monte Carlo (AFQMC) method. The EKT allows for the direct calculation of electron addition and removal spectral functions using reduced density matrices of the N-particle system and avoids the need for analytic continuation. The lowest level of EKT with AFQMC, called EKT1-AFQMC, is benchmarked using atoms, small molecules, 14-electron and 54-electron uniform electron gas supercells, and a minimal unit cell model of diamond at the Γ-point. Via comparison with numerically exact results (when possible) and coupled-cluster methods, we find that EKT1-AFQMC can reproduce the qualitative features of spectral functions for Koopmans-like charge excitations with errors in peak locations of less than 0.25 eV in a finite basis. We also note the numerical difficulties that arise in the EKT1-AFQMC eigenvalue problem, especially when back-propagated quantities are very noisy. We show how a systematic higher-order EKT approach can correct errors in EKT1-based theories with respect to the satellite region of the spectral function. Our work will be of use for the study of low-energy charge excitations and spectral functions in correlated molecules and solids where AFQMC can be reliably performed for both energy and back propagation.