Van der Waals coefficients beyond the classical shell model
Abstract
Van der Waals (vdW) coefficients can be accurately generated and understood by modelling the dynamic multipole polarizability of each interacting object. Accurate static polarizabilities are the key to accurate dynamic polarizabilities and vdW coefficients. In this work, we present and study in detail a hollowsphere model for the dynamic multipole polarizability proposed recently by two of the present authors (JT and JPP) to simulate the vdW coefficients for inhomogeneous systems that allow for a cavity. The inputs to this model are the accurate static multipole polarizabilities and the electron density. A simplification of the full hollowsphere model, the singlefrequency approximation (SFA), circumvents the need for a detailed electron density and for a double numerical integration over space. We find that the hollowsphere model in SFA is not only accurate for nanoclusters and cage molecules (e.g., fullerenes) but also yields vdW coefficients among atoms, fullerenes, and small clusters in good agreement with expensive timedependent density functional calculations. However, the classical shell model (CSM), which inputs the static dipole polarizabilities and estimates the static higherorder multipole polarizabilities therefrom, is accurate for the higherorder vdW coefficients only when the interacting objects are large. For the lowestorder vdW coefficient C{sub 6}, SFA and CSMmore »
 Authors:

 Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 191046323 (United States)
 Department of Physics and Engineering Physics, Tulane University, New Orleans, Louisiana 70118 (United States)
 Department of Chemistry and Department of Physics and Astronomy, Rice University, Houston, Texas 772511892, USA and Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21589 (Saudi Arabia)
 Department of Physics, Temple University, Philadelphia, Pennsylvania 19122 (United States)
 Publication Date:
 OSTI Identifier:
 22415836
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 142; Journal Issue: 2; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 00219606
 Country of Publication:
 United States
 Language:
 English
 Subject:
 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; APPROXIMATIONS; ATOMS; COMPUTERIZED SIMULATION; DENSITY FUNCTIONAL METHOD; DIPOLES; ELECTRON DENSITY; FULLERENES; MOLECULAR CRYSTALS; MOLECULES; NANOSTRUCTURES; POLARIZABILITY; TIME DEPENDENCE; VAN DER WAALS FORCES
Citation Formats
Tao, Jianmin, Fang, Yuan, Hao, Pan, Scuseria, G. E., Ruzsinszky, Adrienn, and Perdew, John P. Van der Waals coefficients beyond the classical shell model. United States: N. p., 2015.
Web. doi:10.1063/1.4905259.
Tao, Jianmin, Fang, Yuan, Hao, Pan, Scuseria, G. E., Ruzsinszky, Adrienn, & Perdew, John P. Van der Waals coefficients beyond the classical shell model. United States. doi:10.1063/1.4905259.
Tao, Jianmin, Fang, Yuan, Hao, Pan, Scuseria, G. E., Ruzsinszky, Adrienn, and Perdew, John P. Wed .
"Van der Waals coefficients beyond the classical shell model". United States. doi:10.1063/1.4905259.
@article{osti_22415836,
title = {Van der Waals coefficients beyond the classical shell model},
author = {Tao, Jianmin and Fang, Yuan and Hao, Pan and Scuseria, G. E. and Ruzsinszky, Adrienn and Perdew, John P.},
abstractNote = {Van der Waals (vdW) coefficients can be accurately generated and understood by modelling the dynamic multipole polarizability of each interacting object. Accurate static polarizabilities are the key to accurate dynamic polarizabilities and vdW coefficients. In this work, we present and study in detail a hollowsphere model for the dynamic multipole polarizability proposed recently by two of the present authors (JT and JPP) to simulate the vdW coefficients for inhomogeneous systems that allow for a cavity. The inputs to this model are the accurate static multipole polarizabilities and the electron density. A simplification of the full hollowsphere model, the singlefrequency approximation (SFA), circumvents the need for a detailed electron density and for a double numerical integration over space. We find that the hollowsphere model in SFA is not only accurate for nanoclusters and cage molecules (e.g., fullerenes) but also yields vdW coefficients among atoms, fullerenes, and small clusters in good agreement with expensive timedependent density functional calculations. However, the classical shell model (CSM), which inputs the static dipole polarizabilities and estimates the static higherorder multipole polarizabilities therefrom, is accurate for the higherorder vdW coefficients only when the interacting objects are large. For the lowestorder vdW coefficient C{sub 6}, SFA and CSM are exactly the same. The higherorder (C{sub 8} and C{sub 10}) terms of the vdW expansion can be almost as important as the C{sub 6} term in molecular crystals. Application to a variety of clusters shows that there is strong nonadditivity of the longrange vdW interactions between nanoclusters.},
doi = {10.1063/1.4905259},
journal = {Journal of Chemical Physics},
issn = {00219606},
number = 2,
volume = 142,
place = {United States},
year = {2015},
month = {1}
}