Skip to main content

Lund University Publications

LUND UNIVERSITY LIBRARIES

A theoretical study of the solvent shift to the n -> pi* transition in formaldehyde with an effective discrete quantum chemical solvent model including non-electrostatic perturbation

Öhrn, Anders and Karlström, Gunnar LU (2006) In Molecular Physics 104(19). p.3087-3099
Abstract
An effective solvent model with an explicit solvent representation is described. The modelled perturbation of the solute due to the discrete solvent molecules includes polarization and a non-electrostatic interaction. The latter depends on the overlap between the solute wave function and the solvent orbitals and approximately accounts for the restraint the Pauli principle puts on the space which the solute wave function is allowed to occupy, and consequently also models the exchange repulsion between solute and solvent. The wave function of the solute is a linear combination with variational coefficients of orthogonal states obtained with the complete active space state interaction (CASSI) method. With this model, the solvent shift to the... (More)
An effective solvent model with an explicit solvent representation is described. The modelled perturbation of the solute due to the discrete solvent molecules includes polarization and a non-electrostatic interaction. The latter depends on the overlap between the solute wave function and the solvent orbitals and approximately accounts for the restraint the Pauli principle puts on the space which the solute wave function is allowed to occupy, and consequently also models the exchange repulsion between solute and solvent. The wave function of the solute is a linear combination with variational coefficients of orthogonal states obtained with the complete active space state interaction (CASSI) method. With this model, the solvent shift to the n ->pi* transition in hydrated formaldehyde is studied and the analysis of the results investigates the different contributions to the total shift; the non-electrostatic interaction is found to be of significance and capable of coupling with the electrostatic interaction in qualitatively different ways for the ground and first excited state. Solvent density distributions for hydrated formaldehyde are also reported. (Less)
Please use this url to cite or link to this publication:
author
and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Molecular Physics
volume
104
issue
19
pages
3087 - 3099
publisher
Taylor & Francis
external identifiers
  • wos:000241662100010
  • scopus:33750593551
ISSN
1362-3028
DOI
10.1080/00268970600965629
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
03b9367e-f8d0-431c-9f97-db3835d5d648 (old id 378689)
date added to LUP
2016-04-01 11:34:07
date last changed
2021-09-29 03:13:15
@article{03b9367e-f8d0-431c-9f97-db3835d5d648,
  abstract     = {An effective solvent model with an explicit solvent representation is described. The modelled perturbation of the solute due to the discrete solvent molecules includes polarization and a non-electrostatic interaction. The latter depends on the overlap between the solute wave function and the solvent orbitals and approximately accounts for the restraint the Pauli principle puts on the space which the solute wave function is allowed to occupy, and consequently also models the exchange repulsion between solute and solvent. The wave function of the solute is a linear combination with variational coefficients of orthogonal states obtained with the complete active space state interaction (CASSI) method. With this model, the solvent shift to the n ->pi* transition in hydrated formaldehyde is studied and the analysis of the results investigates the different contributions to the total shift; the non-electrostatic interaction is found to be of significance and capable of coupling with the electrostatic interaction in qualitatively different ways for the ground and first excited state. Solvent density distributions for hydrated formaldehyde are also reported.},
  author       = {Öhrn, Anders and Karlström, Gunnar},
  issn         = {1362-3028},
  language     = {eng},
  number       = {19},
  pages        = {3087--3099},
  publisher    = {Taylor & Francis},
  series       = {Molecular Physics},
  title        = {A theoretical study of the solvent shift to the n -> pi* transition in formaldehyde with an effective discrete quantum chemical solvent model including non-electrostatic perturbation},
  url          = {http://dx.doi.org/10.1080/00268970600965629},
  doi          = {10.1080/00268970600965629},
  volume       = {104},
  year         = {2006},
}