Communication: Accurate higherorder van der Waals coefficients between molecules from a model dynamic multipole polarizability
Abstract
Due to the absence of the longrange van der Waals (vdW) interaction, conventional density functional theory (DFT) often fails in the description of molecular complexes and solids. In recent years, considerable progress has been made in the development of the vdW correction. However, the vdW correction based on the leadingorder coefficient C{sub 6} alone can only achieve limited accuracy, while accurate modeling of higherorder coefficients remains a formidable task, due to the strong nonadditivity effect. Here, we apply a model dynamic multipole polarizability within a modified singlefrequency approximation to calculate C{sub 8} and C{sub 10} between small molecules. We find that the higherorder vdW coefficients from this model can achieve remarkable accuracy, with mean absolute relative deviations of 5% for C{sub 8} and 7% for C{sub 10}. Inclusion of accurate higherorder contributions in the vdW correction will effectively enhance the predictive power of DFT in condensed matter physics and quantum chemistry.
 Authors:

 Department of Physics, Temple University, Philadelphia, Pennsylvania 19122 (United States)
 Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 191046323 (United States)
 Publication Date:
 OSTI Identifier:
 22493652
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 144; Journal Issue: 3; Other Information: (c) 2016 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 00219606
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ACCURACY; CARBON; CHEMISTRY; COMPUTERIZED SIMULATION; CORRECTIONS; DENSITY FUNCTIONAL METHOD; INCLUSIONS; MOLECULES; POLARIZABILITY; SOLIDS; VAN DER WAALS FORCES
Citation Formats
Tao, Jianmin, and Rappe, Andrew M. Communication: Accurate higherorder van der Waals coefficients between molecules from a model dynamic multipole polarizability. United States: N. p., 2016.
Web. doi:10.1063/1.4940397.
Tao, Jianmin, & Rappe, Andrew M. Communication: Accurate higherorder van der Waals coefficients between molecules from a model dynamic multipole polarizability. United States. doi:10.1063/1.4940397.
Tao, Jianmin, and Rappe, Andrew M. Thu .
"Communication: Accurate higherorder van der Waals coefficients between molecules from a model dynamic multipole polarizability". United States. doi:10.1063/1.4940397.
@article{osti_22493652,
title = {Communication: Accurate higherorder van der Waals coefficients between molecules from a model dynamic multipole polarizability},
author = {Tao, Jianmin and Rappe, Andrew M.},
abstractNote = {Due to the absence of the longrange van der Waals (vdW) interaction, conventional density functional theory (DFT) often fails in the description of molecular complexes and solids. In recent years, considerable progress has been made in the development of the vdW correction. However, the vdW correction based on the leadingorder coefficient C{sub 6} alone can only achieve limited accuracy, while accurate modeling of higherorder coefficients remains a formidable task, due to the strong nonadditivity effect. Here, we apply a model dynamic multipole polarizability within a modified singlefrequency approximation to calculate C{sub 8} and C{sub 10} between small molecules. We find that the higherorder vdW coefficients from this model can achieve remarkable accuracy, with mean absolute relative deviations of 5% for C{sub 8} and 7% for C{sub 10}. Inclusion of accurate higherorder contributions in the vdW correction will effectively enhance the predictive power of DFT in condensed matter physics and quantum chemistry.},
doi = {10.1063/1.4940397},
journal = {Journal of Chemical Physics},
issn = {00219606},
number = 3,
volume = 144,
place = {United States},
year = {2016},
month = {1}
}