School of Chemistry, University of Leeds, Leeds LS2 9JT, UK.
Phys Chem Chem Phys. 2013 Oct 14;15(38):16227-35. doi: 10.1039/c3cp51199e. Epub 2013 Sep 2.
We report the first results of ab initio multiconfigurational Ehrenfest simulations of pyrrole photodynamics. We note that, in addition to the two intersections of 1(1)A2 and 1(1)B1 states with the ground state 1(1)A1, which are known to be responsible for N-H bond fission, another intersection between the 1(2)A2 and 1(2)B1 states of the resulting molecular radical becomes important after the departure of the H atom. This intersection, which is effectively between the two lowest electronic states of the pyrrolyl radical, may play a significant role in explaining the branching ratio between the two states observed experimentally. The exchange of population between the two states of pyrrolyl occurs on a longer scale than that of N-H bond fission.
我们报告了从头算多组态 Ehrenfest 模拟吡咯光动力学生成的初步结果。我们注意到，除了已知负责 N-H 键断裂的 1(1)A2 和 1(1)B1 态与基态 1(1)A1 的两个交叉点外，在 H 原子离开后，生成的分子自由基的 1(2)A2 和 1(2)B1 态之间的另一个交叉点变得很重要。这个交叉点实际上是吡咯自由基的两个最低电子态之间的交叉点，可能在解释实验观测到的两个态之间的分支比方面发挥重要作用。吡咯自由基两个态之间的人口交换比 N-H 键断裂的交换规模更长。
