Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging
Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging
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DOI：
10.1039/c4cp04571h
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发表时间：
2015-01-01
影响因子：
3.3
通讯作者：
Shalashilin, Dmitrii V.
中科院分区：
文献类型：
--
作者：
Makhov, Dmitry V.;Saita, Kenichiro;Shalashilin, Dmitrii V.
我们报告了一个详细的计算模拟的光解吡咯使用从头算多重克隆（AIMC）方法在MOLPRO中实现。AIMC实现的效率，采用训练基集、矩阵元素的线性逼近和Ehrenfest配置克隆，使我们能够积累重要的统计数据。计算并分析了吡咯的总动能释放谱（TKER）和速度图成像（VMI），并与实验测量结果进行了直接比较。TKER谱和速度图（VMI）的结构都得到了很好的再现。以前，人们认为VMI的各向同性成分来自于长时间的统计解离。相反，我们的模拟表明，超快动力学对TKER谱的低能和高能部分都有重要贡献。
We report a detailed computational simulation of the photodissociation of pyrrole using the ab initio Multiple Cloning (AIMC) method implemented within MOLPRO. The efficiency of the AIMC implementation, employing train basis sets, linear approximation for matrix elements, and Ehrenfest configuration cloning, allows us to accumulate significant statistics. We calculate and analyze the total kinetic energy release (TKER) spectrum and Velocity Map Imaging (VMI) of pyrrole and compare the results directly with experimental measurements. Both the TKER spectrum and the structure of the velocity map image (VMI) are well reproduced. Previously, it has been assumed that the isotropic component of the VMI arises from long time statistical dissociation. Instead, our simulations suggest that ultrafast dynamics contributes significantly to both low and high energy portions of the TKER spectrum.