The many-body expansion for aqueous systems revisited: 1. Water-water interactions

Heindel, Joseph; Xantheas, Sotiris S.

doi:10.1021/acs.jctc.9b00749

Title: The many-body expansion for aqueous systems revisited: 1. Water-water interactions

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Abstract

We revisit the Many-Body Expansion (MBE) for water-water interactions by examining the effects of the basis set, including those resulting from the Basis Set Superposition Error (BSSE) correction, on the various terms for selected sizes of water clusters up to n = 21. The analysis is performed at the second order Møller-Plesset (MP2) perturbation theory with the family of augmented correlation consistent basis sets up to five zeta quality for the (H2O)n, n = 7, 10, 13, 16 and 21 clusters, for which we report either the complete MBE (n = 7, 10) or the one through the 6-body (n = 13) and the 5-body terms (n = 16, 21). Our results suggest that any sizeable contributions to the total cluster binding energy arising from the 5-body and larger terms are solely an artifact of the size of the basis set. Indeed, all terms above the 4-body converge monotonically to practically zero at the Complete Basis Set (CBS) limit. The magnitudes of the 5-body and above terms are accurately reproduced even with the smaller basis set of the series (aug-cc-pVDZ) once the BSSE correction is taken into account. The same level of theory (MP2/aug-cc-pVDZ, BSSEcorrected) also accurately reproduces the MP2/CBSmore »« less

Authors:

Heindel, Joseph ^[1];

^[2]

University of Washington
BATTELLE (PACIFIC NW LAB)

Publication Date:: Tue Nov 10 00:00:00 EST 2020

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1721703

Report Number(s):: PNNL-SA-145771

DOE Contract Number:: AC05-76RL01830

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Theory and Computation

Additional Journal Information:: Journal Volume: 16; Journal Issue: 11

Country of Publication:: United States

Language:: English

Citation Formats


                    Heindel, Joseph, and Xantheas, Sotiris S. The many-body expansion for aqueous systems revisited: 1. Water-water interactions.  United States: N. p., 2020. 
        Web.  doi:10.1021/acs.jctc.9b00749.

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                    Heindel, Joseph, & Xantheas, Sotiris S. The many-body expansion for aqueous systems revisited: 1. Water-water interactions.  United States.  https://doi.org/10.1021/acs.jctc.9b00749

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                    Heindel, Joseph, and Xantheas, Sotiris S. 2020.  
        "The many-body expansion for aqueous systems revisited: 1. Water-water interactions".  United States.  https://doi.org/10.1021/acs.jctc.9b00749.

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@article{osti_1721703,

  title        = {The many-body expansion for aqueous systems revisited: 1. Water-water interactions},

  author       = {Heindel, Joseph and Xantheas, Sotiris S.},

  abstractNote = {We revisit the Many-Body Expansion (MBE) for water-water interactions by examining the effects of the basis set, including those resulting from the Basis Set Superposition Error (BSSE) correction, on the various terms for selected sizes of water clusters up to n = 21. The analysis is performed at the second order Møller-Plesset (MP2) perturbation theory with the family of augmented correlation consistent basis sets up to five zeta quality for the (H2O)n, n = 7, 10, 13, 16 and 21 clusters, for which we report either the complete MBE (n = 7, 10) or the one through the 6-body (n = 13) and the 5-body terms (n = 16, 21). Our results suggest that any sizeable contributions to the total cluster binding energy arising from the 5-body and larger terms are solely an artifact of the size of the basis set. Indeed, all terms above the 4-body converge monotonically to practically zero at the Complete Basis Set (CBS) limit. The magnitudes of the 5-body and above terms are accurately reproduced even with the smaller basis set of the series (aug-cc-pVDZ) once the BSSE correction is taken into account. The same level of theory (MP2/aug-cc-pVDZ, BSSEcorrected) also accurately reproduces the MP2/CBS values of the 3- and 4-body terms. The contribution of electron correlation to the 3- and 4-body terms is quite small, so that neglecting the correlation contribution in all terms above the 3-body results in an error of ??(0.1%). The BSSE correction to the largest 2-body term in the MBE was accurately estimated from the function ?? [1 + erf(-?? ??)], which is proportional to the common (overlapping) area between two Gaussian distributions whose centers are separated by R, with the constants ??, ?? fitted to the calculated BSSE corrections for the individual 2-body terms of the clusters with each basis set. Our results unquestionably demonstrate that the MBE for water-water interactions converges to the 4-body term, since any finite terms above the 4-body are artifacts of the size of the basis set and can be safely truncated at the 4-body term when either a very large basis set is used or BSSE corrections are taken into account even with the aug-cc-pVDZ basis set. We expect these findings to have important consequences in the pursuit of accurate many-body molecular dynamics simulations for aqueous systems.},

  doi          = {10.1021/acs.jctc.9b00749},

  url          = {https://www.osti.gov/biblio/1721703},
  journal      = {Journal of Chemical Theory and Computation},
number       = 11,

  volume       = 16,

  place        = {United States},

  year         = {Tue Nov 10 00:00:00 EST 2020},

  month        = {Tue Nov 10 00:00:00 EST 2020}

}

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