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Title: Prediction of correlation energies using variational subspace valence bond

Abstract

In the variational subspace valence bond (VSVB) [G. D. Fletcher, J. Chem. Phys. 142, 134112 (2015)] method, the electronic orbitals comprising the wave function correspond to chemically meaningful objects, such as bonds, lone pairs, atomic cores, and so on. Selected regions of a molecule (for example, a single chemical bond, as opposed to all the bonds) can be modeled with different levels of basis set and possible methods for modeling correlation from the other regions. The interactions between the components of a molecule (say, a bond and a neighboring orbital) can then be studied in detail for their impact on a chemical phenomenon while avoiding the expense of necessarily applying the higher levels and methods to the entire molecule. Here, this work presents the theoretical basis for modeling correlation effects between specific electron pairs by incorporating terms in the inter-electronic coordinates (“r12”) into VSVB. The approach is validated with calculations on small systems using single-reference wave functions.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [3]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Computational Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Argonne Leadership Computing Facility
  3. Intel® Corporation, Schaumburg, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1894138
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 157; Journal Issue: 12; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical bonding; geminal wavefunction; electronic correlation; electronic structure methods; valence bond theory; quantum chemistry; dihydrogen; correlation energy

Citation Formats

Fletcher, Graham D., Bertoni, Colleen, Keceli, Murat, and D’Mello, Michael J. Prediction of correlation energies using variational subspace valence bond. United States: N. p., 2022. Web. doi:10.1063/5.0098146.
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Fletcher, Graham D., Bertoni, Colleen, Keceli, Murat, & D’Mello, Michael J. Prediction of correlation energies using variational subspace valence bond. United States. https://doi.org/10.1063/5.0098146
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Fletcher, Graham D., Bertoni, Colleen, Keceli, Murat, and D’Mello, Michael J. Tue . "Prediction of correlation energies using variational subspace valence bond". United States. https://doi.org/10.1063/5.0098146. https://www.osti.gov/servlets/purl/1894138.
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@article{osti_1894138,
title = {Prediction of correlation energies using variational subspace valence bond},
author = {Fletcher, Graham D. and Bertoni, Colleen and Keceli, Murat and D’Mello, Michael J.},
abstractNote = {In the variational subspace valence bond (VSVB) [G. D. Fletcher, J. Chem. Phys. 142, 134112 (2015)] method, the electronic orbitals comprising the wave function correspond to chemically meaningful objects, such as bonds, lone pairs, atomic cores, and so on. Selected regions of a molecule (for example, a single chemical bond, as opposed to all the bonds) can be modeled with different levels of basis set and possible methods for modeling correlation from the other regions. The interactions between the components of a molecule (say, a bond and a neighboring orbital) can then be studied in detail for their impact on a chemical phenomenon while avoiding the expense of necessarily applying the higher levels and methods to the entire molecule. Here, this work presents the theoretical basis for modeling correlation effects between specific electron pairs by incorporating terms in the inter-electronic coordinates (“r12”) into VSVB. The approach is validated with calculations on small systems using single-reference wave functions.},
doi = {10.1063/5.0098146},
journal = {Journal of Chemical Physics},
number = 12,
volume = 157,
place = {United States},
year = {Tue Aug 30 00:00:00 EDT 2022},
month = {Tue Aug 30 00:00:00 EDT 2022}
}
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https://doi.org/10.1063/5.0098146
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