Ab initio multiple spawning on laser-dressed states: a study of 1,3-cyclohexadiene photoisomerization via light-induced conical intersections

作者：Kim Jaehee^*; Tao Hongli; Martinez Todd J; Buck**aum Phil

来源：Journal of Physics B: Atomic, Molecular and Optical Physics , 2015, 48(16): 164003.

DOI：10.1088/0953-4075/48/16/164003

• ab initio multiple spawning
• light induced conical intersections
• coherent control
• photoisomerization
• 1,3-cyclohexadiene

We extend the ab initio multiple spawning method to include both field-free and field-induced nonadiabatic transitions. We apply this method to describe ultrafast pump-probe experiments of the photoinduced ring-opening of gas phase 1,3-cyclohexadiene. In the absence of a control field, nonadiabatic transitions mediated by a conical intersection (CoIn) lead to rapid ground state recovery with both 1,3-cyclohexadiene and ring-opened hexatriene products. However, application of a control field within the first 200 fs after photoexcitation results in suppression of the hexatriene product. We demonstrate that this is a consequence of population dumping prior to reaching the CoIn and further interpret this in terms of light-induced CoIns created by the control field.

• 出版日期2015-8-28