Spin-orbit ab initio investigation of the ultraviolet photolysis of diiodomethane
(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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https://lup.lub.lu.se/record/662745
- author
- Liu, Ya-Jun LU ; De Vico, Luca LU ; Lindh, Roland LU and Fang, Wei-Hai
- organization
- publishing date
- 2007
- 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 (<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}}, }