Evaluation of the excitation spectra with diffusion Monte Carlo on an auxiliary bosonic ground state

Fernando A Reboredo; Paul R C Kent; Jaron T Krogel

doi:10.1063/5.0155513

Evaluation of the excitation spectra with diffusion Monte Carlo on an auxiliary bosonic ground state

J Chem Phys. 2023 Sep 21;159(11):114118. doi: 10.1063/5.0155513.

Authors

Fernando A Reboredo¹, Paul R C Kent², Jaron T Krogel¹

Affiliations

¹ Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
² Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.

PMID: 37724730
DOI: 10.1063/5.0155513

Abstract

We aim to improve upon the variational Monte Carlo (VMC) approach for excitations replacing the Jastrow factor by an auxiliary bosonic (AB) ground state and multiplying it by a fermionic component factor. The instantaneous change in imaginary time of an arbitrary excitation in the original interacting fermionic system is obtained by measuring observables via the ground-state distribution of walkers of an AB system that is subject to an auxiliary effective potential. The effective potential is used to (i) drive the AB system's ground-state configuration space toward the configuration space of the excitations of the original fermionic system and (ii) subtract from a diffusion Monte Carlo (DMC) calculation contributions that can be included in conventional approximations, such as mean-field and configuration interaction (CI) methods. In this novel approach, the AB ground state is treated statistically in DMC, whereas the fermionic component of the original system is expanded in a basis. The excitation energies of the fermionic eigenstates are obtained by sampling a fermion-boson coupling term on the AB ground state. We show that this approach can take advantage of and correct for approximate eigenstates obtained via mean-field calculations or truncated interactions. We demonstrate that the AB ground-state factor incorporates the correlations missed by standard Jastrow factors, further reducing basis truncation errors. Relevant parts of the theory have been tested in soluble model systems and exhibit excellent agreement with exact analytical data and CI and VMC approaches. In particular, for limited basis set expansions and sufficient statistics, AB approaches outperform CI and VMC in terms of basis size for the same systems. The implementation of this method in current codes, despite being demanding, will be facilitated by reusing procedures already developed for calculating ground-state properties with DMC and excitations with VMC.