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Spin-orbit ab initio investigation of the ultraviolet photolysis of diiodomethane

Liu, Ya-Jun LU ; De Vico, Luca LU ; Lindh, Roland LU and Fang, Wei-Hai (2007) In ChemPhysChem 8(6). p.890-898
Abstract
The UV photodissociation (<5 eV) of diiodomethane (CH(2)l(2)) is investigated by spin-orbit ab inito calculations. The experimentally observed photodissociation channels in the gas and condensed phases are clearly assigned by multi-state second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space-state interaction potential energy curves. The calculated results indicate that the fast dissociations of the first two singlet states of CH(2)l(2) and CH(2)l-l lead to geminate-radical products, CH(2)l(+) +l(P-2(3/2)) or CH(2)l(+) + l*(P-2(1/2)). The recombination process from CH(2)l-l to CH(2)l(2) is explained by an isomerazation process and a secondary photodissociation... (More)
The UV photodissociation (<5 eV) of diiodomethane (CH(2)l(2)) is investigated by spin-orbit ab inito calculations. The experimentally observed photodissociation channels in the gas and condensed phases are clearly assigned by multi-state second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space-state interaction potential energy curves. The calculated results indicate that the fast dissociations of the first two singlet states of CH(2)l(2) and CH(2)l-l lead to geminate-radical products, CH(2)l(+) +l(P-2(3/2)) or CH(2)l(+) + l*(P-2(1/2)). The recombination process from CH(2)l-l to CH(2)l(2) is explained by an isomerazation process and a secondary photodissociation reaction of CH(2)l-l. Finally, the study reveals that spin-orbits effects are sifnificant in the quantitative analysis of the electronic spectrum of the CH(2)l-l species. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
reaction mechanisms, photochemistry, isomerization, ab initio calculations, absorption
in
ChemPhysChem
volume
8
issue
6
pages
890 - 898
publisher
John Wiley & Sons
external identifiers
  • wos:000246190900013
  • scopus:34248146572
ISSN
1439-7641
DOI
10.1002/cphc.200600737
language
English
LU publication?
yes
id
caa75857-03e9-4d0a-9545-115e380d89d2 (old id 662745)
date added to LUP
2007-12-13 09:01:10
date last changed
2017-07-23 03:47:42
@article{caa75857-03e9-4d0a-9545-115e380d89d2,
  abstract     = {The UV photodissociation (&lt;5 eV) of diiodomethane (CH(2)l(2)) is investigated by spin-orbit ab inito calculations. The experimentally observed photodissociation channels in the gas and condensed phases are clearly assigned by multi-state second-order multiconfigurational perturbation theory in conjunction with spin-orbit interaction through complete active space-state interaction potential energy curves. The calculated results indicate that the fast dissociations of the first two singlet states of CH(2)l(2) and CH(2)l-l lead to geminate-radical products, CH(2)l(+) +l(P-2(3/2)) or CH(2)l(+) + l*(P-2(1/2)). The recombination process from CH(2)l-l to CH(2)l(2) is explained by an isomerazation process and a secondary photodissociation reaction of CH(2)l-l. Finally, the study reveals that spin-orbits effects are sifnificant in the quantitative analysis of the electronic spectrum of the CH(2)l-l species.},
  author       = {Liu, Ya-Jun and De Vico, Luca and Lindh, Roland and Fang, Wei-Hai},
  issn         = {1439-7641},
  keyword      = {reaction mechanisms,photochemistry,isomerization,ab initio calculations,absorption},
  language     = {eng},
  number       = {6},
  pages        = {890--898},
  publisher    = {John Wiley & Sons},
  series       = {ChemPhysChem},
  title        = {Spin-orbit ab initio investigation of the ultraviolet photolysis of diiodomethane},
  url          = {http://dx.doi.org/10.1002/cphc.200600737},
  volume       = {8},
  year         = {2007},
}