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Full Configuration Interaction Excited-State Energies in Large Active Spaces from Subspace Iteration with Repeated Random Sparsification

Greene, Samuel M. and Webber, Robert J. and Smith, James E. T. and Weare, Jonathan and Berkelbach, Timothy C. (2022) Full Configuration Interaction Excited-State Energies in Large Active Spaces from Subspace Iteration with Repeated Random Sparsification. Journal of Chemical Theory and Computation, 18 (12). pp. 7218-7232. ISSN 1549-9618. doi:10.1021/acs.jctc.2c00435.

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We present a stable and systematically improvable quantum Monte Carlo (QMC) approach to calculating excited-state energies, which we implement using our fast randomized iteration method for the full configuration interaction problem (FCI-FRI). Unlike previous excited-state quantum Monte Carlo methods, our approach, which is based on an asymmetric variant of subspace iteration, avoids the use of dot products of random vectors and instead relies upon trial vectors to maintain orthogonality and estimate eigenvalues. By leveraging recent advances, we apply our method to calculate ground- and excited-state energies of challenging molecular systems in large active spaces, including the carbon dimer with 8 electrons in 108 orbitals (8e,108o), an oxo-Mn(salen) transition metal complex (28e,28o), ozone (18e,87o), and butadiene (22e,82o). In the majority of these test cases, our approach yields total excited-state energies that agree with those from state-of-the-art methods─including heat-bath CI, the density matrix renormalization group approach, and FCIQMC─to within sub-milliHartree accuracy. In all cases, estimated excitation energies agree to within about 0.1 eV.

Item Type:Article
Related URLs:
URLURL TypeDescription
Greene, Samuel M.0000-0001-5135-5926
Webber, Robert J.0000-0001-8286-6315
Smith, James E. T.0000-0002-5130-8633
Berkelbach, Timothy C.0000-0002-7445-2136
Additional Information:The authors thank Aaron Dinner, Michael Lindsey, and Verena Neufeld for useful conversations and Benjamin Pritchard for his suggestions for improving the readability and performance of our code. S.M.G. was supported by a software fellowship from the Molecular Sciences Software Institute, which is funded by U.S. National Science Foundation grant OAC-1547580. R.J.W. was supported by New York University’s Dean’s Dissertation Fellowship and by the National Science Foundation through award DMS-1646339. J.W. acknowledges support from the Advanced Scientific Computing Research Program within the DOE Office of Science through award DE-SC0020427. The Flatiron Institute is a division of the Simons Foundation.
Funding AgencyGrant Number
New York University (NYU)UNSPECIFIED
Department of Energy (DOE)DE-SC0020427
Simons FoundationUNSPECIFIED
Issue or Number:12
Record Number:CaltechAUTHORS:20221128-494761600.56
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:118092
Deposited By: Research Services Depository
Deposited On:21 Dec 2022 17:54
Last Modified:21 Dec 2022 17:54

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