Visible Absorption Spectra and Two-Photon Photodissociation of Halobenzene Cations in Solid Argon

Article abstract of DOI:10.1021/ja00394a016

Matrix photoionization experiments with bromobenzene, chlorobenzene, and fluorobenzene precursors produced absorptions dur to bromobenzene cation at 505 +/- 5 nm, chlorobenzene cation at 470 +/- 2 nm, and fluorobenzene cation at 431 +/- 1 nm, respectively, in excellent agreement with gas-phase photodissociation and photoelectron spectra.Two-photon dissosiation of the bromobenzene cation in solid argon was affected by photolysis in the very strong visible n₂ ->? charge-transfer electronic transition, as found in earlier gas-phase work.The lack of significant two-photon dissociation of fluorobenzene cation is attributed to lower oscillator strength for the ?->? transition corresponding to absorption of the first photon.