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

Research output: Contribution to journalArticle

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.

Details

Authors
  • Ya-Jun Liu
  • Luca De Vico
  • Roland Lindh
  • Wei-Hai Fang
Organisations
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Theoretical Chemistry

Keywords

  • reaction mechanisms, photochemistry, isomerization, ab initio calculations, absorption
Original languageEnglish
Pages (from-to)890-898
JournalChemPhysChem
Volume8
Issue number6
Publication statusPublished - 2007
Publication categoryResearch
Peer-reviewedYes

Bibliographic note

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)