VUV Photofragmentation of Chloroiodomethane: The Iso-CH₂I-Cl and Iso-CH₂Cl-I Radical Cation Formation.

ABSTRACT: Dihalomethanes XCH₂Y (X and Y = F, Cl, Br, and I) are a class of compounds involved in several processes leading to the release of halogen atoms, ozone consumption, and aerosol particle formation. Neutral dihalomethanes have been largely studied, but chemical physics properties and processes involving their radical ions, like the pathways of their decomposition, have not been completely investigated. In this work the photodissociation dynamics of the ClCH₂I molecule has been explored in the photon energy range 9-21 eV using both VUV rare gas discharge lamps and synchrotron radiation. The experiments show that, among the different fragment ions, CH₂I⁺ and CH₂Cl⁺, which correspond to the Cl- and I-losses, respectively, play a dominant role. The experimental ionization energy of ClCH₂I and the appearance energies of the CH₂I⁺ and CH₂Cl⁺ ions are in agreement with the theoretical results obtained at the MP2/CCSD(T) level of theory. Computational investigations have been also performed to study the isomerization of geminal [ClCH₂I]^•+ into the iso-chloroiodomethane isomers: [CH₂I-Cl]^•+ and [CH₂Cl-I]^•+.

SUBMITTER: Casavola AR 

PROVIDER: S-EPMC8010789 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature