吡咯分子II第一吸收带的光解离动力学。$^1\!A_2(πσ^*) \leftarrow \tilde{X}^1\!A_1(ππ)$跃迁的光碎片分布
Photodissociation dynamics in the first absorption band of pyrrole: II. Photofragment distributions for the $^1\!A_2(πσ^*) \leftarrow \tilde{X}^1\!A_1(ππ)$ transition
摘要：
本文对吡咯分子在基态$^1\!A_2(πσ^*)$中光解形成的光碎片吡咯基+H原子的总动能释放进行了分析。TKER分布包含与宽漫吸收光谱相比的关于碎裂过程的补充且通常更精确的信息。的分布计算量子力学的非绝热态$^1\!A_2(πσ^*)$无论是孤立的或耦合到地面的电子状态在出口通道圆锥形交叉。计算中使用了新的从头算准非绝热势能矩阵。介绍了一种基于近似重叠积分的绝热映射方法，利用该方法可以高效、准确地再现量子力学TKER分布。最后，将计算的TKER与实验结果进行了比较。再现了测量的振动分辨分布的主要特征，并对谱峰进行了详细的归属和解释。
英文摘要：
The analysis of the total kinetic energy release (TKER) of the photofragments pyrrolyl + H-atom formed in the photodissociation of pyrrole in the low-lying state $^1\!A_2(πσ^*)$ is presented. The TKER distributions contain complementary and often more precise information on the fragmentation process than the broad diffuse absorption spectra. The distributions are calculated quantum mechanically for the diabatic state $^1\!A_2(πσ^*)$ either isolated or coupled to the ground electronic state at an exit channel conical intersection. The calculations use the novel ab initio quasi-diabatic potential energy matrix constructed in paper I. The approximate overlap integral-based adiabatic mapping approach is introduced with which the quantum mechanical TKER distributions can be efficiently and accurately reproduced. Finally, the calculated TKERs are compared with the experimental results. The main features of the measured vibrationally resolved distributions are reproduced, and the spectral peaks are assigned and interpreted in detail.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
