Beyond Walkers in Stochastic Quantum Chemistry: Reducing Error Using Fast Randomized Iteration

Samuel M. Greene, Robert J. Webber, Jonathan Weare, Timothy C. Berkelbach

Research output: Contribution to journalArticle

Abstract

We introduce a family of methods for the full configuration interaction problem in quantum chemistry, based on the fast randomized iteration (FRI) framework [Lim, L.-H.; Weare, J. SIAM Rev.2017, 59, 547; DOI: 10.1137/15M1040827 ]. These methods, which we term "FCI-FRI", stochastically impose sparsity during iterations of the power method and can be viewed as a generalization of full configuration interaction quantum Monte Carlo (FCIQMC) without walkers. In addition to the multinomial scheme commonly used to sample excitations in FCIQMC, we present a systematic scheme where excitations are not sampled independently. Performing ground-state calculations on five small molecules at fixed cost, we find that the systematic FCI-FRI scheme is 11-45 times more statistically efficient than the multinomial FCI-FRI scheme, which is in turn 1.4-178 times more statistically efficient than the original FCIQMC algorithm.

Original languageEnglish (US)
Pages (from-to)4834-4850
Number of pages17
JournalJournal of chemical theory and computation
Volume15
Issue number9
DOIs
StatePublished - Sep 10 2019

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Quantum chemistry
quantum chemistry
Ground state
iteration
configuration interaction
Molecules
Costs
excitation
costs
ground state
molecules

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Beyond Walkers in Stochastic Quantum Chemistry : Reducing Error Using Fast Randomized Iteration. / Greene, Samuel M.; Webber, Robert J.; Weare, Jonathan; Berkelbach, Timothy C.

In: Journal of chemical theory and computation, Vol. 15, No. 9, 10.09.2019, p. 4834-4850.

Research output: Contribution to journalArticle

Greene, Samuel M. ; Webber, Robert J. ; Weare, Jonathan ; Berkelbach, Timothy C. / Beyond Walkers in Stochastic Quantum Chemistry : Reducing Error Using Fast Randomized Iteration. In: Journal of chemical theory and computation. 2019 ; Vol. 15, No. 9. pp. 4834-4850.
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