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pi* -> n fluorescence transition in formaldehyde in aqueous solution: A combined quantum chemical statistical mechanical study

Öhrn, Anders LU and Karlström, Gunnar LU (2006) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 110(5). p.1934-1942
Abstract
The solvent shift to the fluorescence transition pi* -> n in formaldehyde in aqueous Solution is theoretically analyzed. The solvent model has explicit representation of the solvent and uses the complete active space state interaction (CASSI) method to obtain a description of the wave function of the solute similar to what the complete active space self-consistent-field (CASSCF) method would give. In the description of-the solute-solvent interaction the discrete set of solvent molecules perturb the Solute not only through an electrostatic perturbation but also through a nonelectrostatic operator. The latter describes in a way analogous to pseudopotential theory the effect the Pauli principle has on the solute embedded in the solvent.... (More)
The solvent shift to the fluorescence transition pi* -> n in formaldehyde in aqueous Solution is theoretically analyzed. The solvent model has explicit representation of the solvent and uses the complete active space state interaction (CASSI) method to obtain a description of the wave function of the solute similar to what the complete active space self-consistent-field (CASSCF) method would give. In the description of-the solute-solvent interaction the discrete set of solvent molecules perturb the Solute not only through an electrostatic perturbation but also through a nonelectrostatic operator. The latter describes in a way analogous to pseudopotential theory the effect the Pauli principle has on the solute embedded in the solvent. This way the exchange repulsion between solute and solvent is accounted for which therefore can be anisotropic. The best estimate of the average shift is a blue shift of 0.003 eV, and for the current transition the nonelectrostatic perturbation broadens the distribution but has no significant effect on the average shift. (Less)
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publication status
published
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in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
110
issue
5
pages
1934 - 1942
publisher
The American Chemical Society (ACS)
external identifiers
  • wos:000235297400032
  • scopus:33644793455
ISSN
1520-5215
DOI
10.1021/jp055678l
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
bb7b6274-705c-4d96-acc5-fab17330d5d9 (old id 417727)
date added to LUP
2016-04-01 15:48:53
date last changed
2021-09-08 03:24:02
@article{bb7b6274-705c-4d96-acc5-fab17330d5d9,
  abstract     = {The solvent shift to the fluorescence transition pi* -> n in formaldehyde in aqueous Solution is theoretically analyzed. The solvent model has explicit representation of the solvent and uses the complete active space state interaction (CASSI) method to obtain a description of the wave function of the solute similar to what the complete active space self-consistent-field (CASSCF) method would give. In the description of-the solute-solvent interaction the discrete set of solvent molecules perturb the Solute not only through an electrostatic perturbation but also through a nonelectrostatic operator. The latter describes in a way analogous to pseudopotential theory the effect the Pauli principle has on the solute embedded in the solvent. This way the exchange repulsion between solute and solvent is accounted for which therefore can be anisotropic. The best estimate of the average shift is a blue shift of 0.003 eV, and for the current transition the nonelectrostatic perturbation broadens the distribution but has no significant effect on the average shift.},
  author       = {Öhrn, Anders and Karlström, Gunnar},
  issn         = {1520-5215},
  language     = {eng},
  number       = {5},
  pages        = {1934--1942},
  publisher    = {The American Chemical Society (ACS)},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {pi* -> n fluorescence transition in formaldehyde in aqueous solution: A combined quantum chemical statistical mechanical study},
  url          = {http://dx.doi.org/10.1021/jp055678l},
  doi          = {10.1021/jp055678l},
  volume       = {110},
  year         = {2006},
}