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Radiative singlet-triplet transition properties from coupled-cluster response theory: The importance of the S-0 -> T-1 transition for the photodissociation of water at 193 nm

Christiansen, Ove LU and Gauss, J (2002) In Journal of Chemical Physics 116(15). p.6674-6686
Abstract
Expressions for first-order induced electronic transition matrix elements are derived within the coupled-cluster response theory framework. When combined with electric-dipole and spin-orbit operators, these matrix elements allow the calculation of radiative transition probabilities between singlet ground and triplet excited states. An implementation employing an atomic mean-field representation of the spin-orbit operator is presented at the coupled-cluster singles and doubles level. The suitability of this operator for the calculation of radiative transition probabilities is checked in test calculations for BH and AlH which are compared to full configuration interaction results obtained with the full Breit-Pauli spin-orbit operator. In a... (More)
Expressions for first-order induced electronic transition matrix elements are derived within the coupled-cluster response theory framework. When combined with electric-dipole and spin-orbit operators, these matrix elements allow the calculation of radiative transition probabilities between singlet ground and triplet excited states. An implementation employing an atomic mean-field representation of the spin-orbit operator is presented at the coupled-cluster singles and doubles level. The suitability of this operator for the calculation of radiative transition probabilities is checked in test calculations for BH and AlH which are compared to full configuration interaction results obtained with the full Breit-Pauli spin-orbit operator. In a first application, we investigate the importance of the S-0-->T-1 transition relative to the S-0-->S-1 transition in the first absorption band of the electronic spectrum of H2O. The potential importance of the S-0-->T-1 transition for understanding the photodissociation in the low energy regime of this band is confirmed and accurate estimates are given for the energy difference between the S-1 and T-1 state as well as the transition dipole moments for excitations to these states. In addition, the geometry dependence of these properties is analyzed. (C) 2002 American Institute of Physics. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
116
issue
15
pages
6674 - 6686
publisher
American Institute of Physics
external identifiers
  • wos:000174767200033
  • scopus:0037091146
ISSN
0021-9606
DOI
10.1063/1.1460867
language
English
LU publication?
yes
id
892484f8-aa3b-40fb-9538-fbc721086614 (old id 340633)
date added to LUP
2007-08-14 15:56:11
date last changed
2017-01-01 05:03:36
@article{892484f8-aa3b-40fb-9538-fbc721086614,
  abstract     = {Expressions for first-order induced electronic transition matrix elements are derived within the coupled-cluster response theory framework. When combined with electric-dipole and spin-orbit operators, these matrix elements allow the calculation of radiative transition probabilities between singlet ground and triplet excited states. An implementation employing an atomic mean-field representation of the spin-orbit operator is presented at the coupled-cluster singles and doubles level. The suitability of this operator for the calculation of radiative transition probabilities is checked in test calculations for BH and AlH which are compared to full configuration interaction results obtained with the full Breit-Pauli spin-orbit operator. In a first application, we investigate the importance of the S-0-->T-1 transition relative to the S-0-->S-1 transition in the first absorption band of the electronic spectrum of H2O. The potential importance of the S-0-->T-1 transition for understanding the photodissociation in the low energy regime of this band is confirmed and accurate estimates are given for the energy difference between the S-1 and T-1 state as well as the transition dipole moments for excitations to these states. In addition, the geometry dependence of these properties is analyzed. (C) 2002 American Institute of Physics.},
  author       = {Christiansen, Ove and Gauss, J},
  issn         = {0021-9606},
  language     = {eng},
  number       = {15},
  pages        = {6674--6686},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Radiative singlet-triplet transition properties from coupled-cluster response theory: The importance of the S-0 -> T-1 transition for the photodissociation of water at 193 nm},
  url          = {http://dx.doi.org/10.1063/1.1460867},
  volume       = {116},
  year         = {2002},
}