A theory for the photodissociation of polyatomic molecules, with application to CF3I
A theory for the photodissociation of polyatomic molecules, with application to CF3I
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DOI：
10.1063/1.450051
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发表时间：
1986-04
影响因子：
4.4
通讯作者：
D. Clary
中科院分区：
文献类型：
--
作者：
D. Clary
本文描述了一种计算大于三原子的多原子分子光解离谱的理论。一般的方法结合了振动紧密耦合，旋转无限阶突然近似与Kulander和Light的技术来计算光解积分。三维理论使多原子光碎片中的几个振动态耦合在一起，并且还允许母体分子中的初始振动和旋转激发。该方法已被应用于CF 3 I → CF 3 +I（2 P1/2）光解过程的辐射频率范围为32 000-42 000 cm−1。横截面CF 3 I在基态振动状态，也与C-I的拉伸和弯曲模式最初激发。相当大的振动激发的CF 3光碎片中获得的计算在较高的频率，这一发现是在协议与实验测量。有一个显着的优惠人口的CF 3组合…
A theory is described for calculating photodissociation spectra for polyatomic molecules larger than triatomics. The general method combines the vibrational close‐coupling, rotational infinite‐order‐sudden approximation with the technique of Kulander and Light for calculating photodissociation integrals. The three‐dimensional theory enables several vibrational states in the polyatomic photofragments to be coupled together and also allows for initial vibrational and rotational excitation in the parent molecule. The method has been applied to the CF3I→CF3+I (2P1/2) photodissociation process for the radiation frequency range 32 000–42 000 cm−1. Cross sections are reported for CF3I in the ground vibrational state, and also with C–I stretching and bending modes excited initially. Considerable vibrational excitation in the CF3 photofragments is obtained in the calculations at higher frequencies, a finding that is in agreement with experimental measurements. There is a marked preferential population of CF3 combi...