Multireference theoretical investigation on selectivity of the bond fissions in photodissociation of acetyl cyanide

作者：Xiao Hong Yan; Liu Ya Jun^*; Fang Wei Hai

来源：Journal of Chemical Physics, 2007, 127(24): 244313.

DOI：10.1063/1.2814169

The selectivity of the C-CH(3) and C-CN bond fissions upon excitation of acetyl cyanide at 193 nm has been investigated at the theoretical level of multistate complete active space self-consistent field second order perturbation. The calculated results indicated that the initially excited S(3) state relaxes to S(2) via ultrafast internal conversion. The S(2) state could dissociate via two pathways. One, adiabatically dissociates to CH(3)CO(X)+CN(A). The other one internally converts to S(1) before S(1) intersystem crossing to T(1). The T(1) state subsequently dissociates to two groups of products: CH(3)(X)+OCCN(X) and CH(3)CO(X)+CN(X). The experimentally observed preference branching of CN elimination over CH(3) one and bond selectivity are the results of the competition between the adiabatic and nonadiabatic dynamics of the S(2) state.

• 出版日期2007-12-28
• 单位北京师范大学