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Title: Multipole moments in the effective fragment potential method

Abstract

In the effective fragment potential (EFP) method the Coulomb potential is represented using a set of multipole moments generated by the distributed multipole analysis (DMA) method. Misquitta, Stone, and Fazeli recently developed a basis space-iterated stockholder atom (BS-ISA) method to generate multipole moments. This study assesses the accuracy of the EFP interaction energies using sets of multipole moments generated from the BS-ISA method, and from several versions of the DMA method (such as analytic and numeric grid-based), with varying basis sets. Both methods lead to reasonable results, although using certain implementations of the DMA method can result in large errors. With respect to the CCSD(T)/CBS interaction energies, the mean unsigned error (MUE) of the EFP method for the S22 data set using BS-ISA–generated multipole moments and DMA-generated multipole moments (using a small basis set and the analytic DMA procedure) is 0.78 and 0.72 kcal/mol, respectively. Here, the MUE accuracy is on the same order as MP2 and SCS-MP2. The MUEs are lower than in a previous study benchmarking the EFP method without the EFP charge transfer term, demonstrating that the charge transfer term increases the accuracy of the EFP method. Regardless of the multipole moment method used, it is likelymore » that much of the error is due to an insufficient short-range electrostatic term (i.e., charge penetration term), as shown by comparisons with symmetry-adapted perturbation theory.« less

Authors:
 [1];  [2];  [3]; ORCiD logo [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
  2. Purdue Univ., West Lafayette, IN (United States)
  3. Univ. of London, London (England)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1355900
Report Number(s):
IS-J-9325
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
CHE-1465154; AC02-07CH11358
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 9; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bertoni, Colleen, Slipchenko, Lyudmila V., Misquitta, Alston J., and Gordon, Mark S.. Multipole moments in the effective fragment potential method. United States: N. p., 2017. Web. doi:10.1021/acs.jpca.7b00682.
Bertoni, Colleen, Slipchenko, Lyudmila V., Misquitta, Alston J., & Gordon, Mark S.. Multipole moments in the effective fragment potential method. United States. doi:10.1021/acs.jpca.7b00682.
Bertoni, Colleen, Slipchenko, Lyudmila V., Misquitta, Alston J., and Gordon, Mark S.. Fri . "Multipole moments in the effective fragment potential method". United States. doi:10.1021/acs.jpca.7b00682. https://www.osti.gov/servlets/purl/1355900.
@article{osti_1355900,
title = {Multipole moments in the effective fragment potential method},
author = {Bertoni, Colleen and Slipchenko, Lyudmila V. and Misquitta, Alston J. and Gordon, Mark S.},
abstractNote = {In the effective fragment potential (EFP) method the Coulomb potential is represented using a set of multipole moments generated by the distributed multipole analysis (DMA) method. Misquitta, Stone, and Fazeli recently developed a basis space-iterated stockholder atom (BS-ISA) method to generate multipole moments. This study assesses the accuracy of the EFP interaction energies using sets of multipole moments generated from the BS-ISA method, and from several versions of the DMA method (such as analytic and numeric grid-based), with varying basis sets. Both methods lead to reasonable results, although using certain implementations of the DMA method can result in large errors. With respect to the CCSD(T)/CBS interaction energies, the mean unsigned error (MUE) of the EFP method for the S22 data set using BS-ISA–generated multipole moments and DMA-generated multipole moments (using a small basis set and the analytic DMA procedure) is 0.78 and 0.72 kcal/mol, respectively. Here, the MUE accuracy is on the same order as MP2 and SCS-MP2. The MUEs are lower than in a previous study benchmarking the EFP method without the EFP charge transfer term, demonstrating that the charge transfer term increases the accuracy of the EFP method. Regardless of the multipole moment method used, it is likely that much of the error is due to an insufficient short-range electrostatic term (i.e., charge penetration term), as shown by comparisons with symmetry-adapted perturbation theory.},
doi = {10.1021/acs.jpca.7b00682},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 9,
volume = 121,
place = {United States},
year = {Fri Feb 17 00:00:00 EST 2017},
month = {Fri Feb 17 00:00:00 EST 2017}
}

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