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Title: Using full configuration interaction quantum Monte Carlo in a seniority zero space to investigate the correlation energy equivalence of pair coupled cluster doubles and doubly occupied configuration interaction

Abstract

Over the past few years, pair coupled cluster doubles (pCCD) has shown promise for the description of strong correlation. This promise is related to its apparent ability to match results from doubly occupied configuration interaction (DOCI), even though the latter method has exponential computational cost. Here, by modifying the full configuration interaction quantum Monte Carlo algorithm to sample only the seniority zero sector of Hilbert space, we show that the DOCI and pCCD energies are in agreement for a variety of 2D Hubbard models, including for systems well out of reach for conventional configuration interaction algorithms. Our calculations are aided by the sign problem being much reduced in the seniority zero space compared with the full space. We present evidence for this and then discuss the sign problem in terms of the wave function of the system which appears to have a simplified sign structure.

Authors:
;  [1]
  1. Department of Chemistry and Department of Physics and Astronomy, Rice University, Houston, Texas 77005-1892 (United States)
Publication Date:
OSTI Identifier:
22660881
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 9; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPUTERIZED SIMULATION; CONFIGURATION INTERACTION; ELECTRON CORRELATION; HILBERT SPACE; HUBBARD MODEL; MONTE CARLO METHOD; WAVE FUNCTIONS

Citation Formats

Shepherd, James J., E-mail: jamesjshepherd@gmail.com, Henderson, Thomas M., and Scuseria, Gustavo E. Using full configuration interaction quantum Monte Carlo in a seniority zero space to investigate the correlation energy equivalence of pair coupled cluster doubles and doubly occupied configuration interaction. United States: N. p., 2016. Web. doi:10.1063/1.4942770.
Shepherd, James J., E-mail: jamesjshepherd@gmail.com, Henderson, Thomas M., & Scuseria, Gustavo E. Using full configuration interaction quantum Monte Carlo in a seniority zero space to investigate the correlation energy equivalence of pair coupled cluster doubles and doubly occupied configuration interaction. United States. https://doi.org/10.1063/1.4942770
Shepherd, James J., E-mail: jamesjshepherd@gmail.com, Henderson, Thomas M., and Scuseria, Gustavo E. 2016. "Using full configuration interaction quantum Monte Carlo in a seniority zero space to investigate the correlation energy equivalence of pair coupled cluster doubles and doubly occupied configuration interaction". United States. https://doi.org/10.1063/1.4942770.
@article{osti_22660881,
title = {Using full configuration interaction quantum Monte Carlo in a seniority zero space to investigate the correlation energy equivalence of pair coupled cluster doubles and doubly occupied configuration interaction},
author = {Shepherd, James J., E-mail: jamesjshepherd@gmail.com and Henderson, Thomas M. and Scuseria, Gustavo E.},
abstractNote = {Over the past few years, pair coupled cluster doubles (pCCD) has shown promise for the description of strong correlation. This promise is related to its apparent ability to match results from doubly occupied configuration interaction (DOCI), even though the latter method has exponential computational cost. Here, by modifying the full configuration interaction quantum Monte Carlo algorithm to sample only the seniority zero sector of Hilbert space, we show that the DOCI and pCCD energies are in agreement for a variety of 2D Hubbard models, including for systems well out of reach for conventional configuration interaction algorithms. Our calculations are aided by the sign problem being much reduced in the seniority zero space compared with the full space. We present evidence for this and then discuss the sign problem in terms of the wave function of the system which appears to have a simplified sign structure.},
doi = {10.1063/1.4942770},
url = {https://www.osti.gov/biblio/22660881}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 9,
volume = 144,
place = {United States},
year = {2016},
month = {3}
}

Works referencing / citing this record:

Method for making 2-electron response reduced density matrices approximately N -representable
journal, February 2018


Pair 2-electron reduced density matrix theory using localized orbitals
journal, August 2017


Polynomial-product states: A symmetry-projection-based factorization of the full coupled cluster wavefunction in terms of polynomials of double excitations
journal, April 2019