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Solvent effects on rotatory strength tensors. 1. Theory and application of the combined coupled cluster/dielectric continuum model

Kongsted, Jacob LU ; Pedersen, Thomas LU ; Osted, A; Hansen, A E; Mikkelsen, K V and Christiansen, Ove LU (2004) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 108(16). p.3632-3641
Abstract
In this article we present the first theoretical study of solvent effects on the rotatory strength tensor. The system chosen is solvated formaldehyde for which only one tensor element is nonvanishing, and the solvent is modeled as a linear, homogeneous, and isotropic dielectric continuum. We present results using both an equilibrium and a nonequilibrium description of the solvent. Four illustrative solvents (ethyl ether, acetone, methanol, and water) are considered together with the corresponding results for formaldehyde in vacuum. We utilize the following ab initio methods: the coupled cluster model including singles and doubles (CCSD) and the coupled cluster second-order approximate singles and doubles (M). Furthermore, we compare the... (More)
In this article we present the first theoretical study of solvent effects on the rotatory strength tensor. The system chosen is solvated formaldehyde for which only one tensor element is nonvanishing, and the solvent is modeled as a linear, homogeneous, and isotropic dielectric continuum. We present results using both an equilibrium and a nonequilibrium description of the solvent. Four illustrative solvents (ethyl ether, acetone, methanol, and water) are considered together with the corresponding results for formaldehyde in vacuum. We utilize the following ab initio methods: the coupled cluster model including singles and doubles (CCSD) and the coupled cluster second-order approximate singles and doubles (M). Furthermore, we compare the coupled cluster results with the corresponding uncorrelated self-consistent-field (SCF) results. In addition to the rotatory strength tensor we also present solvent effects on the low-lying electronic excitation energies and corresponding ordinary intensities using both the length and velocity gauges. We find that both correlation and solvent effects have a significant influence on the transition properties. The introduction of the solvent is, in some cases, found to result in a sign change of the rotatory strength tensor elements which clearly demonstrates the importance of a proper description of the solvent influence on this property. (Less)
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author
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
108
issue
16
pages
3632 - 3641
publisher
The American Chemical Society
external identifiers
  • scopus:2342633797
ISSN
1520-5215
DOI
10.1021/jp037836j
language
English
LU publication?
no
id
7ff32920-333d-497c-9afb-0b7fed6dc387 (old id 139678)
date added to LUP
2007-07-17 11:34:42
date last changed
2016-06-29 09:04:12
@article{7ff32920-333d-497c-9afb-0b7fed6dc387,
  abstract     = {In this article we present the first theoretical study of solvent effects on the rotatory strength tensor. The system chosen is solvated formaldehyde for which only one tensor element is nonvanishing, and the solvent is modeled as a linear, homogeneous, and isotropic dielectric continuum. We present results using both an equilibrium and a nonequilibrium description of the solvent. Four illustrative solvents (ethyl ether, acetone, methanol, and water) are considered together with the corresponding results for formaldehyde in vacuum. We utilize the following ab initio methods: the coupled cluster model including singles and doubles (CCSD) and the coupled cluster second-order approximate singles and doubles (M). Furthermore, we compare the coupled cluster results with the corresponding uncorrelated self-consistent-field (SCF) results. In addition to the rotatory strength tensor we also present solvent effects on the low-lying electronic excitation energies and corresponding ordinary intensities using both the length and velocity gauges. We find that both correlation and solvent effects have a significant influence on the transition properties. The introduction of the solvent is, in some cases, found to result in a sign change of the rotatory strength tensor elements which clearly demonstrates the importance of a proper description of the solvent influence on this property.},
  author       = {Kongsted, Jacob and Pedersen, Thomas and Osted, A and Hansen, A E and Mikkelsen, K V and Christiansen, Ove},
  issn         = {1520-5215},
  language     = {eng},
  number       = {16},
  pages        = {3632--3641},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Solvent effects on rotatory strength tensors. 1. Theory and application of the combined coupled cluster/dielectric continuum model},
  url          = {http://dx.doi.org/10.1021/jp037836j},
  volume       = {108},
  year         = {2004},
}