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Title: Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures

Abstract

Nanostructures can be bound together at equilibrium by the van der Waals (vdW) effect, a small but ubiquitous many-body attraction that presents challenges to density functional theory. How does the binding energy depend upon the size or number of atoms in one of a pair of identical nanostructures? To answer this question, we treat each nanostructure properly as a whole object, not as a collection of atoms. Our calculations start from an accurate static dipole polarizability for each considered nanostructure, and an accurate equilibrium center-to-center distance for the pair (the latter from experiment, or from the vdW-DF-cx functional). We consider the competition in each term $$-C_{2k}/d^{2k}$$ ($k=3, 4, 5$) of the long-range vdW series for the interaction energy, between the size dependence of the vdW coefficient $$C_{2k}$$ and that of the $2k$-th power of the center-to-center distance $d$. The damping of these vdW terms can be negligible, but in any case it does not affect the size dependence for a given term in the absence of non-vdW binding. To our surprise, the vdW energy can be size-independent for quasi-spherical nanoclusters bound to one another by vdW interaction, even with strong nonadditivity of the vdW coefficient, as demonstrated for fullerenes. We also show that, for low-dimensional systems, the vdW interaction yields the strongest size-dependence, in stark contrast to that of fullerenes. We illustrate this with parallel planar polycyclic aromatic hydrocarbons. Other cases are between, as shown by sodium clusters.

Authors:
ORCiD logo [1]
  1. Temple Univ., Philadelphia, PA (United States). Dept. of Physics
Publication Date:
Research Org.:
Temple Univ., Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1419407
Grant/Contract Number:  
SC0018194
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
99 GENERAL AND MISCELLANEOUS; van der Waals interaction; DFT

Citation Formats

Tao, Jianmin. Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures. United States: N. p., 2018. Web. doi:10.1063/1.5018572.
Tao, Jianmin. Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures. United States. doi:10.1063/1.5018572.
Tao, Jianmin. Wed . "Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures". United States. doi:10.1063/1.5018572. https://www.osti.gov/servlets/purl/1419407.
@article{osti_1419407,
title = {Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures},
author = {Tao, Jianmin},
abstractNote = {Nanostructures can be bound together at equilibrium by the van der Waals (vdW) effect, a small but ubiquitous many-body attraction that presents challenges to density functional theory. How does the binding energy depend upon the size or number of atoms in one of a pair of identical nanostructures? To answer this question, we treat each nanostructure properly as a whole object, not as a collection of atoms. Our calculations start from an accurate static dipole polarizability for each considered nanostructure, and an accurate equilibrium center-to-center distance for the pair (the latter from experiment, or from the vdW-DF-cx functional). We consider the competition in each term $-C_{2k}/d^{2k}$ ($k=3, 4, 5$) of the long-range vdW series for the interaction energy, between the size dependence of the vdW coefficient $C_{2k}$ and that of the $2k$-th power of the center-to-center distance $d$. The damping of these vdW terms can be negligible, but in any case it does not affect the size dependence for a given term in the absence of non-vdW binding. To our surprise, the vdW energy can be size-independent for quasi-spherical nanoclusters bound to one another by vdW interaction, even with strong nonadditivity of the vdW coefficient, as demonstrated for fullerenes. We also show that, for low-dimensional systems, the vdW interaction yields the strongest size-dependence, in stark contrast to that of fullerenes. We illustrate this with parallel planar polycyclic aromatic hydrocarbons. Other cases are between, as shown by sodium clusters.},
doi = {10.1063/1.5018572},
journal = {Journal of Chemical Physics},
number = 7,
volume = 148,
place = {United States},
year = {2018},
month = {2}
}

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