Combined nonadiabatic transition-state theory and ab initio molecular dynamics study on selectivity of the α and β bond fissions in photodissociation of bromoacetyl chloride

Feng Zhang; Wan-Jian Ding; Wei-Hai Fang
November 2006
Journal of Chemical Physics;11/14/2006, Vol. 125 Issue 18, p184305
Academic Journal
The selectivity of the α C–Cl and β C–Br bond fissions upon n→π* excitation of bromoacetyl chloride has been investigated with combined nonadiabatic Rice-Ramsperger-Kassel-Marcus theory and ab initio molecular dynamics calculations, which are based on the potential energy profiles calculated with the complete active space self-consistent field and multireference configuration interaction methods. The Zhu-Nakamura [J. Chem. Phys. 101, 10630 (1994); 102, 7448 (1995)] theory is chosen to calculate the nonadiabatic hopping probability. It is found that nonadiabatic effect plays an important role in determining selective dissociations of the C–Cl and C–Br bonds. The calculated rate constants are close to those from experimentally inferred values, but the branching ratio of the α C–Cl and β C–Br bond fissions is different from the experimental findings. The direct molecular dynamics calculations predict that fission of the C–Cl bond occurs on a time scale of picoseconds and cleavage of the β C–Br bond proceeds with less probability within the same period. This reveals that the initial relaxation dynamics is probably another important factor that influences the selectivity of the C–Cl and C–Br bond fissions in photodissociation of BrCH2COCl at 248 nm.


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