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An intramolecular induction correction model of the molecular dipole moment.

Holt, Asbjörn LU and Karlström, Gunnar LU (2008) In Journal of Computational Chemistry 29(7). p.1084-1091
Abstract
A model for intramolecular polarization is presented. It is used to describe the changes in the molecular charge distribution occurring as a response to changes of dihedral angles in the molecule. The model is based on a multicenter multipole distribution of the molecular charge distribution. The electric field from this charge distribution induce dipole moments in the same molecule. The model contains atom type parameters to describe the damping of the electric field. A total of four atom types are used. The parameters are fitted to a calibration set with various functional groups, and tested against a validation set. The error obtained for the calibration set is reduced by 92% and by 88% for the validation set, if compared to an accurate... (More)
A model for intramolecular polarization is presented. It is used to describe the changes in the molecular charge distribution occurring as a response to changes of dihedral angles in the molecule. The model is based on a multicenter multipole distribution of the molecular charge distribution. The electric field from this charge distribution induce dipole moments in the same molecule. The model contains atom type parameters to describe the damping of the electric field. A total of four atom types are used. The parameters are fitted to a calibration set with various functional groups, and tested against a validation set. The error obtained for the calibration set is reduced by 92% and by 88% for the validation set, if compared to an accurate state-of-the-art force field. It is shown that rotating the non-polarizable multicenter multipole distribution for the equilibrium geometry gives too large dipole moments for dihedral angles deviating from the equilibrium geometry. This will lead to too large long-range attractions in simulations. This problem is overcome by using the dipole polarizability correction suggested here, which gives dipole moments very close to the Hartree-Fock dipole moments obtained from reference calculations. (c) 2007 Wiley Periodicals, Inc. J Comput Chem 2007. (Less)
Please use this url to cite or link to this publication:
author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Computational Chemistry
volume
29
issue
7
pages
1084 - 1091
publisher
John Wiley & Sons
external identifiers
  • pmid:18069665
  • wos:000255606400007
  • scopus:42449100891
ISSN
1096-987X
DOI
10.1002/jcc.20867
language
English
LU publication?
yes
id
4822c136-5eeb-449e-bb2f-b15639ce2b91 (old id 1035413)
alternative location
http://www.ncbi.nlm.nih.gov/pubmed/18069665?dopt=Abstract
date added to LUP
2009-07-08 15:42:57
date last changed
2017-01-01 06:32:25
@article{4822c136-5eeb-449e-bb2f-b15639ce2b91,
  abstract     = {A model for intramolecular polarization is presented. It is used to describe the changes in the molecular charge distribution occurring as a response to changes of dihedral angles in the molecule. The model is based on a multicenter multipole distribution of the molecular charge distribution. The electric field from this charge distribution induce dipole moments in the same molecule. The model contains atom type parameters to describe the damping of the electric field. A total of four atom types are used. The parameters are fitted to a calibration set with various functional groups, and tested against a validation set. The error obtained for the calibration set is reduced by 92% and by 88% for the validation set, if compared to an accurate state-of-the-art force field. It is shown that rotating the non-polarizable multicenter multipole distribution for the equilibrium geometry gives too large dipole moments for dihedral angles deviating from the equilibrium geometry. This will lead to too large long-range attractions in simulations. This problem is overcome by using the dipole polarizability correction suggested here, which gives dipole moments very close to the Hartree-Fock dipole moments obtained from reference calculations. (c) 2007 Wiley Periodicals, Inc. J Comput Chem 2007.},
  author       = {Holt, Asbjörn and Karlström, Gunnar},
  issn         = {1096-987X},
  language     = {eng},
  number       = {7},
  pages        = {1084--1091},
  publisher    = {John Wiley & Sons},
  series       = {Journal of Computational Chemistry},
  title        = {An intramolecular induction correction model of the molecular dipole moment.},
  url          = {http://dx.doi.org/10.1002/jcc.20867},
  volume       = {29},
  year         = {2008},
}