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Spin-orbit ab initio study of alkyl halide dissociation via electronic curve crossing

Ajitha, D; Wierzbowska, M; Lindh, Roland LU and Malmqvist, Per-Åke LU (2004) In Journal of Chemical Physics 121(12). p.5761-5766
Abstract
An ab initio study of the role of electronic curve crossing in the photodissociation dynamics of the alkyl halides is presented. Recent experimental studies show that curve crossing plays a deterministic role in deciding the channel of dissociation. Coupled repulsive potential energy curves of the low-lying n-sigma* states are studied including spin-orbit and relativistic effects. Basis set including effect of core correlation is used. Ab initio vertical excitation spectra of CH3I and CF3I are in agreement with the experimental observation. The curve crossing region is around 2.371 Angstrom for CH3I and CF3I. The potential curves of the repulsive excited states have larger slope for CF3I, suggesting a higher velocity and decreased... (More)
An ab initio study of the role of electronic curve crossing in the photodissociation dynamics of the alkyl halides is presented. Recent experimental studies show that curve crossing plays a deterministic role in deciding the channel of dissociation. Coupled repulsive potential energy curves of the low-lying n-sigma* states are studied including spin-orbit and relativistic effects. Basis set including effect of core correlation is used. Ab initio vertical excitation spectra of CH3I and CF3I are in agreement with the experimental observation. The curve crossing region is around 2.371 Angstrom for CH3I and CF3I. The potential curves of the repulsive excited states have larger slope for CF3I, suggesting a higher velocity and decreased intersystem crossing probability on fluorination. We also report the potential curves and the region of curve crossing for CH3Br and CH3Cl. (C) 2004 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
121
issue
12
pages
5761 - 5766
publisher
American Institute of Physics
external identifiers
  • wos:000223872000023
  • scopus:5544229534
ISSN
0021-9606
DOI
10.1063/1.1784411
language
English
LU publication?
yes
id
61d66df8-15f4-4a05-b143-4f8d60100499 (old id 138941)
date added to LUP
2007-06-26 10:02:20
date last changed
2017-07-09 03:42:46
@article{61d66df8-15f4-4a05-b143-4f8d60100499,
  abstract     = {An ab initio study of the role of electronic curve crossing in the photodissociation dynamics of the alkyl halides is presented. Recent experimental studies show that curve crossing plays a deterministic role in deciding the channel of dissociation. Coupled repulsive potential energy curves of the low-lying n-sigma* states are studied including spin-orbit and relativistic effects. Basis set including effect of core correlation is used. Ab initio vertical excitation spectra of CH3I and CF3I are in agreement with the experimental observation. The curve crossing region is around 2.371 Angstrom for CH3I and CF3I. The potential curves of the repulsive excited states have larger slope for CF3I, suggesting a higher velocity and decreased intersystem crossing probability on fluorination. We also report the potential curves and the region of curve crossing for CH3Br and CH3Cl. (C) 2004 American Institute of Physics.},
  author       = {Ajitha, D and Wierzbowska, M and Lindh, Roland and Malmqvist, Per-Åke},
  issn         = {0021-9606},
  language     = {eng},
  number       = {12},
  pages        = {5761--5766},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Spin-orbit ab initio study of alkyl halide dissociation via electronic curve crossing},
  url          = {http://dx.doi.org/10.1063/1.1784411},
  volume       = {121},
  year         = {2004},
}