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Title: Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo

Abstract

Within full configuration interaction quantum Monte Carlo, we investigate how the statistical error behaves as a function of the parameters which control the stochastic sampling. We define the inefficiency as a measure of the statistical error per particle sampling the space and per time step and show there is a sizeable parameter regime where this is minimised. We find that this inefficiency increases sublinearly with Hilbert space size and can be reduced by localising the canonical Hartree–Fock molecular orbitals, suggesting that the choice of basis impacts the method beyond that of the sign problem.

Authors:
;  [1];  [2];  [1]
  1. Department of Chemistry, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom)
  2. Department of Physics, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom)
Publication Date:
OSTI Identifier:
22660879
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:
73 NUCLEAR PHYSICS AND RADIATION PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COMPUTERIZED SIMULATION; CONFIGURATION INTERACTION; HARTREE-FOCK METHOD; HILBERT SPACE; MONTE CARLO METHOD

Citation Formats

Vigor, W. A., Bearpark, M. J., Spencer, J. S., Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ, Thom, A. J. W., and University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW. Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo. United States: N. p., 2016. Web. doi:10.1063/1.4943113.
Vigor, W. A., Bearpark, M. J., Spencer, J. S., Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ, Thom, A. J. W., & University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW. Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo. United States. doi:10.1063/1.4943113.
Vigor, W. A., Bearpark, M. J., Spencer, J. S., Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ, Thom, A. J. W., and University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW. Mon . "Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo". United States. doi:10.1063/1.4943113.
@article{osti_22660879,
title = {Understanding and improving the efficiency of full configuration interaction quantum Monte Carlo},
author = {Vigor, W. A. and Bearpark, M. J. and Spencer, J. S. and Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ and Thom, A. J. W. and University Chemical Laboratory, Lensfield Road, Cambridge CB2 1EW},
abstractNote = {Within full configuration interaction quantum Monte Carlo, we investigate how the statistical error behaves as a function of the parameters which control the stochastic sampling. We define the inefficiency as a measure of the statistical error per particle sampling the space and per time step and show there is a sizeable parameter regime where this is minimised. We find that this inefficiency increases sublinearly with Hilbert space size and can be reduced by localising the canonical Hartree–Fock molecular orbitals, suggesting that the choice of basis impacts the method beyond that of the sign problem.},
doi = {10.1063/1.4943113},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 9,
volume = 144,
place = {United States},
year = {2016},
month = {3}
}