Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

2-2015

Journal or Book Title

Journal of Physical Chemistry A

Volume

119

Issue

10

First Page

2161

Last Page

2168

DOI

10.1021/acs.jpca.5b00379

Abstract

The modeling of dispersion interactions in density functional theory (DFT) is commonly performed using an energy correction that involves empirically fitted parameters for all atom pairs of the system investigated. In this study, the first-principles-derived dispersion energy from the effective fragment potential (EFP) method is implemented for the density functional theory (DFT-D(EFP)) and Hartree–Fock (HF-D(EFP)) energies. Overall, DFT-D(EFP) performs similarly to the semiempirical DFT-D corrections for the test cases investigated in this work. HF-D(EFP) tends to underestimate binding energies and overestimate intermolecular equilibrium distances, relative to coupled cluster theory, most likely due to incomplete accounting for electron correlation. Overall, this first-principles dispersion correction yields results that are in good agreement with coupled-cluster calculations at a low computational cost.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 119 (2015): 2161, doi:10.1021/acs.jpca.5b00379. Copyright 2015 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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