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Vibronic transitions from coupled-cluster response theory: Theory and application to HSiF and H2O

Christiansen, Ove LU ; Ruden, TA; Ruud, K and Helgaker, T (2002) In Journal of Chemical Physics 116(19). p.8334-8342
Abstract
A scheme for calculating the vibrational structure of electronic spectra using coupled-cluster response theory is proposed. To calculate the vibrational structure of electronic transitions, the optimized geometries of the two electronic states, the molecular Hessians, the dipole transition moment and (for vibrationally induced transitions) the geometrical gradient of the dipole transition moment are used in conjunction with a recently developed method for the evaluation of Franck-Condon factors of multidimensional harmonic oscillators. Allowed and vibrationally induced transitions are both described. In this pilot implementation, the required geometrical derivatives are calculated by an automated finite-difference method. The scheme is... (More)
A scheme for calculating the vibrational structure of electronic spectra using coupled-cluster response theory is proposed. To calculate the vibrational structure of electronic transitions, the optimized geometries of the two electronic states, the molecular Hessians, the dipole transition moment and (for vibrationally induced transitions) the geometrical gradient of the dipole transition moment are used in conjunction with a recently developed method for the evaluation of Franck-Condon factors of multidimensional harmonic oscillators. Allowed and vibrationally induced transitions are both described. In this pilot implementation, the required geometrical derivatives are calculated by an automated finite-difference method. The scheme is applied to the 1 (1)A"<--1 (1)A' transition of monofluorosilylene (HSiF) and the vibrationally induced 1 (1)A(2)<--1 (1)A(1) transition of water. (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
19
pages
8334 - 8342
publisher
American Institute of Physics
external identifiers
  • wos:000175297600012
  • scopus:0037088421
ISSN
0021-9606
DOI
10.1063/10.1468639
language
English
LU publication?
yes
id
88fc9d5f-2f11-4382-a9b4-97c2e61a4a1f (old id 339557)
date added to LUP
2007-08-14 15:54:02
date last changed
2017-01-01 04:44:28
@article{88fc9d5f-2f11-4382-a9b4-97c2e61a4a1f,
  abstract     = {A scheme for calculating the vibrational structure of electronic spectra using coupled-cluster response theory is proposed. To calculate the vibrational structure of electronic transitions, the optimized geometries of the two electronic states, the molecular Hessians, the dipole transition moment and (for vibrationally induced transitions) the geometrical gradient of the dipole transition moment are used in conjunction with a recently developed method for the evaluation of Franck-Condon factors of multidimensional harmonic oscillators. Allowed and vibrationally induced transitions are both described. In this pilot implementation, the required geometrical derivatives are calculated by an automated finite-difference method. The scheme is applied to the 1 (1)A"&lt;--1 (1)A' transition of monofluorosilylene (HSiF) and the vibrationally induced 1 (1)A(2)&lt;--1 (1)A(1) transition of water. (C) 2002 American Institute of Physics.},
  author       = {Christiansen, Ove and Ruden, TA and Ruud, K and Helgaker, T},
  issn         = {0021-9606},
  language     = {eng},
  number       = {19},
  pages        = {8334--8342},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Vibronic transitions from coupled-cluster response theory: Theory and application to HSiF and H2O},
  url          = {http://dx.doi.org/10.1063/10.1468639},
  volume       = {116},
  year         = {2002},
}