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Title: Dynamical screening of van der Waals interactions in nanostructured solids: Sublimation of fullerenes

Abstract

Sublimation energy is one of the most important properties of molecular crystals, but it is difficult to study, because the attractive long-range van der Waals (vdW) interaction plays an important role. Here, we apply efficient semilocal density functional theory (DFT), corrected with the dynamically screened vdW interaction (DFT + vdW), the Rutgers-Chalmers nonlocal vdW-DF, and the pairwise-based dispersion-corrected DFT-D2 developed by Grimme and co-workers, to study the sublimation of fullerenes. We find that the short-range part, which accounts for the interaction due to the orbital overlap between fullerenes, is negligibly small. Our calculation shows that there exists a strong screening effect on the vdW interaction arising from the valence electrons of fullerenes. On the other hand, higher-order contributions can be as important as the leading-order term. The reasons are that (i) the surface of fullerene molecules is metallic and thus highly polarizable, (ii) the band gap of fullerene solids is small (less than 2 eV), and (iii) fullerene molecules in the solid phase are so densely packed, yielding the high valence electron density and small equilibrium intermolecular distances (the first nearest neighbor distance is only about 10 Å for C{sub 60}). However, these two effects make opposite contributions, leading tomore » significant error cancellation between these two contributions. We demonstrate that, by considering higher-order contributions and the dynamical screening, the DFT + vdW method can yield sublimation energies of fullerenes in good agreement with reference values, followed by vdW-DF and DFT-D2. The insights from this study are important for a better understanding of the long-range nature of vdW interactions in nanostructured solids.« less

Authors:
; ;  [1]
  1. Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323 (United States)
Publication Date:
OSTI Identifier:
22415706
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 16; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY; DENSITY FUNCTIONAL METHOD; ELECTRONS; EQUILIBRIUM; EV RANGE; FULLERENES; MOLECULAR CRYSTALS; MOLECULES; NANOSTRUCTURES; SOLIDS; SUBLIMATION; SURFACES; VALENCE; VAN DER WAALS FORCES; YIELDS

Citation Formats

Tao, Jianmin, Yang, Jing, and Rappe, Andrew M. Dynamical screening of van der Waals interactions in nanostructured solids: Sublimation of fullerenes. United States: N. p., 2015. Web. doi:10.1063/1.4918761.
Tao, Jianmin, Yang, Jing, & Rappe, Andrew M. Dynamical screening of van der Waals interactions in nanostructured solids: Sublimation of fullerenes. United States. doi:10.1063/1.4918761.
Tao, Jianmin, Yang, Jing, and Rappe, Andrew M. Tue . "Dynamical screening of van der Waals interactions in nanostructured solids: Sublimation of fullerenes". United States. doi:10.1063/1.4918761.
@article{osti_22415706,
title = {Dynamical screening of van der Waals interactions in nanostructured solids: Sublimation of fullerenes},
author = {Tao, Jianmin and Yang, Jing and Rappe, Andrew M.},
abstractNote = {Sublimation energy is one of the most important properties of molecular crystals, but it is difficult to study, because the attractive long-range van der Waals (vdW) interaction plays an important role. Here, we apply efficient semilocal density functional theory (DFT), corrected with the dynamically screened vdW interaction (DFT + vdW), the Rutgers-Chalmers nonlocal vdW-DF, and the pairwise-based dispersion-corrected DFT-D2 developed by Grimme and co-workers, to study the sublimation of fullerenes. We find that the short-range part, which accounts for the interaction due to the orbital overlap between fullerenes, is negligibly small. Our calculation shows that there exists a strong screening effect on the vdW interaction arising from the valence electrons of fullerenes. On the other hand, higher-order contributions can be as important as the leading-order term. The reasons are that (i) the surface of fullerene molecules is metallic and thus highly polarizable, (ii) the band gap of fullerene solids is small (less than 2 eV), and (iii) fullerene molecules in the solid phase are so densely packed, yielding the high valence electron density and small equilibrium intermolecular distances (the first nearest neighbor distance is only about 10 Å for C{sub 60}). However, these two effects make opposite contributions, leading to significant error cancellation between these two contributions. We demonstrate that, by considering higher-order contributions and the dynamical screening, the DFT + vdW method can yield sublimation energies of fullerenes in good agreement with reference values, followed by vdW-DF and DFT-D2. The insights from this study are important for a better understanding of the long-range nature of vdW interactions in nanostructured solids.},
doi = {10.1063/1.4918761},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 16,
volume = 142,
place = {United States},
year = {2015},
month = {4}
}