Comparison of overlap-based models for approximating the exchange-repulsion energy
Söderhjelm, Pär LU ; Karlström, Gunnar LU and Ryde, Ulf LU
(2006)
In Journal of Chemical Physics
124(24).
- Abstract
- Different ways of approximating the exchange-repulsion energy with a classical potential function have been investigated by fitting various expressions to the exact exchange-repulsion energy for a large set of molecular dimers. The expressions involve either the orbital overlap or the electron-density overlap. For comparison, the parameter-free exchange-repulsion model of the effective fragment potential (EFP) is also evaluated. The results show that exchange-repulsion energy is nearly proportional to both the orbital overlap and the density overlap. For accurate results, a distance-dependent correction is needed in both cases. If few parameters are desired, orbital overlap is superior to density overlap, but the fit to density overlap can... (More)
- Different ways of approximating the exchange-repulsion energy with a classical potential function have been investigated by fitting various expressions to the exact exchange-repulsion energy for a large set of molecular dimers. The expressions involve either the orbital overlap or the electron-density overlap. For comparison, the parameter-free exchange-repulsion model of the effective fragment potential (EFP) is also evaluated. The results show that exchange-repulsion energy is nearly proportional to both the orbital overlap and the density overlap. For accurate results, a distance-dependent correction is needed in both cases. If few parameters are desired, orbital overlap is superior to density overlap, but the fit to density overlap can be significantly improved by introducing more parameters. The EFP performs well, except for delocalized pi systems. However, an overlap expression with a few parameters seems to be slightly more accurate and considerably easier to approximate. (c) 2006 American Institute of Physics. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/404519
- author
- Söderhjelm, Pär
LU
; Karlström, Gunnar
LU
and Ryde, Ulf
LU
- organization
- publishing date
- 2006
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 124
- issue
- 24
- article number
- 244101
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- wos:000238730600007
- scopus:33745699625
- ISSN
- 0021-9606
- DOI
- 10.1063/1.2206182
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- 1d78bf28-4e7f-4f21-87d1-993aad3fa102 (old id 404519)
- date added to LUP
- 2016-04-01 11:54:26
- date last changed
- 2023-01-24 02:30:42
@article{1d78bf28-4e7f-4f21-87d1-993aad3fa102,
abstract = {{Different ways of approximating the exchange-repulsion energy with a classical potential function have been investigated by fitting various expressions to the exact exchange-repulsion energy for a large set of molecular dimers. The expressions involve either the orbital overlap or the electron-density overlap. For comparison, the parameter-free exchange-repulsion model of the effective fragment potential (EFP) is also evaluated. The results show that exchange-repulsion energy is nearly proportional to both the orbital overlap and the density overlap. For accurate results, a distance-dependent correction is needed in both cases. If few parameters are desired, orbital overlap is superior to density overlap, but the fit to density overlap can be significantly improved by introducing more parameters. The EFP performs well, except for delocalized pi systems. However, an overlap expression with a few parameters seems to be slightly more accurate and considerably easier to approximate. (c) 2006 American Institute of Physics.}},
author = {{Söderhjelm, Pär and Karlström, Gunnar and Ryde, Ulf}},
issn = {{0021-9606}},
language = {{eng}},
number = {{24}},
publisher = {{American Institute of Physics (AIP)}},
series = {{Journal of Chemical Physics}},
title = {{Comparison of overlap-based models for approximating the exchange-repulsion energy}},
url = {{https://lup.lub.lu.se/search/files/135493608/86_exrep.pdf}},
doi = {{10.1063/1.2206182}},
volume = {{124}},
year = {{2006}},
}