Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2-2014

Journal or Book Title

Journal of Chemical Theory and Computation

Volume

10

Issue

4

First Page

1576

Last Page

1587

DOI

10.1021/ct500017n

Abstract

The R–7 term (E7) in the dispersion expansion is developed in the framework of the general effective fragment potential (EFP2) method, formulated with the dynamic anisotropic Cartesian polarizability tensors over the imaginary frequency range. The E7 formulation is presented in terms of both the total molecular polarizability and the localized molecular orbital (LMO) contributions. An origin transformation from the center of mass to the LMO centroids is incorporated for the computation of the LMO dipole–quadrupole polarizability. The two forms considered for the damping function for the R–7 dispersion interaction, the overlap-based and Tang–Toennies damping functions, are extensions of the existing damping functions for theR–6 term in the dispersion expansion. The R–7 dispersion interaction is highly orientation dependent: it can be either attractive or repulsive, and its magnitude can change substantially as the relative orientation of two interacting molecules changes. Although the R–7 dispersion energy rotationally averages to zero, it may be significant for systems in which rotational averaging does not occur, such as rotationally rigid molecular systems as in molecular solids or constrained surface reactions.

Comments

Reprinted (adapted) with permission from Journal of Chemical Theory and Computation 10 (2014): 1576, doi:10.1021/ct500017n. Copyright 2014 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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