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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
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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 Inc.
external identifiers
  • wos:000246190900013
  • scopus:34248146572
ISSN
1439-7641
DOI
10.1002/cphc.200600737
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
caa75857-03e9-4d0a-9545-115e380d89d2 (old id 662745)
date added to LUP
2016-04-01 12:09:14
date last changed
2023-04-05 01:13:30
@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}},
  keywords     = {{reaction mechanisms; photochemistry; isomerization; ab initio calculations; absorption}},
  language     = {{eng}},
  number       = {{6}},
  pages        = {{890--898}},
  publisher    = {{John Wiley & Sons Inc.}},
  series       = {{ChemPhysChem}},
  title        = {{Spin-orbit ab initio investigation of the ultraviolet photolysis of diiodomethane}},
  url          = {{http://dx.doi.org/10.1002/cphc.200600737}},
  doi          = {{10.1002/cphc.200600737}},
  volume       = {{8}},
  year         = {{2007}},
}