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Title: Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C

Authors:
ORCiD logo; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1364451
Grant/Contract Number:
AC02-05CH11231; FG02-12ER16362
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 23; Related Information: CHORUS Timestamp: 2017-06-20 09:51:11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics
Country of Publication:
United States
Language:
English

Citation Formats

Witte, Jonathon, Neaton, Jeffrey B., and Head-Gordon, Martin. Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C. United States: N. p., 2017. Web. doi:10.1063/1.4986962.
Witte, Jonathon, Neaton, Jeffrey B., & Head-Gordon, Martin. Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C. United States. doi:10.1063/1.4986962.
Witte, Jonathon, Neaton, Jeffrey B., and Head-Gordon, Martin. Wed . "Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C". United States. doi:10.1063/1.4986962.
@article{osti_1364451,
title = {Effective empirical corrections for basis set superposition error in the def2-SVPD basis: gCP and DFT-C},
author = {Witte, Jonathon and Neaton, Jeffrey B. and Head-Gordon, Martin},
abstractNote = {},
doi = {10.1063/1.4986962},
journal = {Journal of Chemical Physics},
number = 23,
volume = 146,
place = {United States},
year = {Wed Jun 21 00:00:00 EDT 2017},
month = {Wed Jun 21 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on June 20, 2018
Publisher's Accepted Manuscript

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  • We report the variation of the binding energy of the formic acid dimer at the CCSD(T)/ Complete Basis Set limit and examine the validity of the BSSE-correction, previously challenged by Kalescky, Kraka and Cremer [J. Chem. Phys. 140 (2014) 084315]. Our best estimate of D0=14.3±0.1 kcal/mol is in excellent agreement with the experimental value of 14.22±0.12 kcal/mol. The BSSE correction is indeed valid for this system since it exhibits the expected behavior of decreasing with increasing basis set size and its inclusion produces the same limit (within 0.1 kcal/mol) as the one obtained from extrapolation of the uncorrected binding energy.more » This work was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. A portion of this research was performed using the Molecular Science Computing Facility (MSCF) in EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research and located at PNNL.« less
  • We report the variation of the binding energy of the Formic Acid Dimer with the size of the basis set at the Coupled Cluster with iterative Singles, Doubles and perturbatively connected Triple replacements [CCSD(T)] level of theory, estimate the Complete Basis Set (CBS) limit, and examine the validity of the Basis Set Superposition Error (BSSE)-correction for this quantity that was previously challenged by Kalescky, Kraka, and Cremer (KKC) [J. Chem. Phys. 140, 084315 (2014)]. Our results indicate that the BSSE correction, including terms that account for the substantial geometry change of the monomers due to the formation of two strongmore » hydrogen bonds in the dimer, is indeed valid for obtaining accurate estimates for the binding energy of this system as it exhibits the expected decrease with increasing basis set size. We attribute the discrepancy between our current results and those of KKC to their use of a valence basis set in conjunction with the correlation of all electrons (i.e., including the 1s of C and O). We further show that the use of a core-valence set in conjunction with all electron correlation converges faster to the CBS limit as the BSSE correction is less than half than the valence electron/valence basis set case. The uncorrected and BSSE-corrected binding energies were found to produce the same (within 0.1 kcal/mol) CBS limits. We obtain CCSD(T)/CBS best estimates for D{sub e} = − 16.1 ± 0.1 kcal/mol and for D{sub 0} = − 14.3 ± 0.1 kcal/mol, the later in excellent agreement with the experimental value of −14.22 ± 0.12 kcal/mol.« less
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  • The inclusion of the fragment relaxation energy terms in the estimation of the basis set superposition error (BSSE) correction to the interaction energy is necessary in order to ensure formal convergence to the uncorrected result at the complete basis set (CBS) limit. The problems associated with their omission are demonstrated for F{sup {minus}}(H{sub 2}O), Cl{sup {minus}}(H{sub 2}O), and (H{sub 2}O){sub 2} especially when very large basis sets are used. The family of correlation consistent basis sets allows for a {ital heuristic} extrapolation of both uncorrected and BSSE-corrected electronic energy differences of the three complexes to the MP2 CBS limits ofmore » {minus}27.1, {minus}15.1, and {minus}4.9 kcal/mol respectively. {copyright} {ital 1996 American Institute of Physics.}« less
  • Our goal in this work was to characterize the importance of basis set superposition error (BSSE) in the reaction energetics of water addition to highly charged metal ions that exhibit strong ion-dipole interactions with water. The gas phase water addition reactions, M(H₂O)³+N + H₂O → M(H₂O)³+N + ₁ [M = La(III), Lu(III); N = 0–8] have been studied, with a particular emphasis on a posteriori methods for calculating BSSE and its constituent energetic components as a function of M(H₂O) ³+N cluster size and water basis set. Because of accumulation of BSSE within the subclusters in the reaction series, the successivemore » reaction counterpoise method for determining the BSSE correction interaction energies is advocated.« less