Departamento de Química, Módulo 13, Facultad de Ciencias, Universidad Autónoma de Madrid, 28049 Madrid, Spain.
Phys Chem Chem Phys. 2019 Oct 24;21(41):23017-23025. doi: 10.1039/c9cp04273c.
The photodissociation dynamics of the ethyl radical following excitation into the 3s and 3p Rydberg states are revisited in a joint experimental and theoretical study. Two different methods to produce the ethyl radical, pyrolysis and in situ photolysis, are employed in order to modify the initial ro-vibrational energy distribution characterizing the ethyl radical beam. H-atom velocity map images following excitation of the radical at 243 nm and at 201 nm are presented and discussed along with ab initio potential energy curves focussing on the bridged C2v geometry. The reported results show that the dynamics following excitation to the 3s Rydberg state is insensitive to the initial internal energy of the parent radical, in contrast to the dynamics on the 3p Rydberg state, which is strongly modified. The role of the bridged C2v geometry on both photodynamics is highlighted and discussed.
在一项联合实验和理论研究中，我们重新研究了乙基自由基在激发到 3s 和 3p Rydberg 态后光离解的动力学。采用两种不同的方法产生乙基自由基，即热解和原位光解，以改变表征乙基自由基束的初始振转能量分布。本文呈现并讨论了在 243nm 和 201nm 处激发自由基后 H 原子速度图图像，以及重点关注桥接 C2v 几何形状的从头算势能曲线。报告的结果表明，与 3p Rydberg 态的动力学强烈改变相比，激发到 3s Rydberg 态后的动力学对母体自由基的初始内部能量不敏感。突出并讨论了桥接 C2v 几何形状对两种光动力学的作用。
