title: A theoretical investigation of the feasibility of Tannor-Rice type control: application to selective bond breakage in gas-phase dihalomethanes.
abstract: Within the B̃ absorption band of CH(2)BrCl, we theoretically analyze the laser-induced control of the Br/Cl branching ratio, Br + CH(2)Cl ← CH(2)BrCl → CH(2)Br + Cl, with CH(2)BrCl initially in its vibrational ground state. For weak-field excitation, the Br/Cl branching ratio increases as a function of wavelength, however, for wavelengths below 180 nm the branching ratio cannot be made smaller than 0.4. Using optimal control theory, we show that the branching ratio can be made significantly less than 0.4, only when very strong fields are employed. Thus, the present work strongly suggests that a Tannor-Rice type laser control mechanism for selective bond breakage in CH(2)BrCl cannot take place without accompanying photoionization.
authors.affiliation: Department of Chemistry, Building 207, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark.
authors.forename: Chuan-Cun
authors.initials: CC
authors.lastname: Shu
authors.forename: Tamás
authors.initials: T
authors.lastname: Rozgonyi
authors.forename: Leticia
authors.initials: L
authors.lastname: González
authors.forename: Niels E
authors.initials: NE
authors.lastname: Henriksen