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Title: Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo

Abstract

We here develop a fully quantum embedded version of initiator full configuration interaction quantum Monte Carlo (i–FCIQMC) and apply it to study an ionic bond (lithium hydride, LiH) and a covalent bond (hydrogen flouride, HF) physisorbed to a benzene molecule. The embedding is performed using a recently developed Huzinaga projection operator approach, which affords good synergy with i–FCIQMC by minimizing the number of orbitals in the calculation. When considering the dissociation energy of these bonds into closed-shell ionic fragments, we find that i–FCIQMC embedded in density functional theory (i–FCIQMC-in-DFT) delivers comparable accuracy with coupled cluster singles and doubles with perturbative triples embedded in density functional theory (CCSD(T)-in-DFT). In treating the bond dissociation energy curve of HF, i–FCIQMC-in-DFT has improved accuracy over CCSD(T)-in-DFT due to the presence of strong correlation. Lastly, we discuss the implications of the new i–FCIQMC-in-DFT method as applied to bond breaking in catalysis.

Authors:
 [1];  [2];  [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Univ. of Iowa, Iowa City, IA (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1720161
Grant/Contract Number:  
SC0008688; FG02-17ER16362; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 15; Journal Issue: 10; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Embedding; Density functional theory; Bond cleavage; Aromatic compounds; Chemical calculations

Citation Formats

Petras, Hayley R., Graham, Daniel S., Ramadugu, Sai Kumar, Goodpaster, Jason D., and Shepherd, James J. Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo. United States: N. p., 2019. Web. doi:10.1021/acs.jctc.9b00571.
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Petras, Hayley R., Graham, Daniel S., Ramadugu, Sai Kumar, Goodpaster, Jason D., & Shepherd, James J. Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo. United States. https://doi.org/10.1021/acs.jctc.9b00571
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Petras, Hayley R., Graham, Daniel S., Ramadugu, Sai Kumar, Goodpaster, Jason D., and Shepherd, James J. Mon . "Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo". United States. https://doi.org/10.1021/acs.jctc.9b00571. https://www.osti.gov/servlets/purl/1720161.
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@article{osti_1720161,
title = {Fully Quantum Embedding with Density Functional Theory for Full Configuration Interaction Quantum Monte Carlo},
author = {Petras, Hayley R. and Graham, Daniel S. and Ramadugu, Sai Kumar and Goodpaster, Jason D. and Shepherd, James J.},
abstractNote = {We here develop a fully quantum embedded version of initiator full configuration interaction quantum Monte Carlo (i–FCIQMC) and apply it to study an ionic bond (lithium hydride, LiH) and a covalent bond (hydrogen flouride, HF) physisorbed to a benzene molecule. The embedding is performed using a recently developed Huzinaga projection operator approach, which affords good synergy with i–FCIQMC by minimizing the number of orbitals in the calculation. When considering the dissociation energy of these bonds into closed-shell ionic fragments, we find that i–FCIQMC embedded in density functional theory (i–FCIQMC-in-DFT) delivers comparable accuracy with coupled cluster singles and doubles with perturbative triples embedded in density functional theory (CCSD(T)-in-DFT). In treating the bond dissociation energy curve of HF, i–FCIQMC-in-DFT has improved accuracy over CCSD(T)-in-DFT due to the presence of strong correlation. Lastly, we discuss the implications of the new i–FCIQMC-in-DFT method as applied to bond breaking in catalysis.},
doi = {10.1021/acs.jctc.9b00571},
journal = {Journal of Chemical Theory and Computation},
number = 10,
volume = 15,
place = {United States},
year = {Mon Aug 26 00:00:00 EDT 2019},
month = {Mon Aug 26 00:00:00 EDT 2019}
}
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https://doi.org/10.1021/acs.jctc.9b00571
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