Signatures of a conical intersection in adiabatic dissociation on the ground electronic state
Signatures of a conical intersection in adiabatic dissociation on the ground electronic state
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地面电子态绝热离解圆锥交点的特征
DOI：
10.1021/jacs.7b11489
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发表时间：
2018
影响因子：
15
通讯作者：
Hua Guo
中科院分区：
文献类型：
--
作者：
Changjian Xie;Christopher L Malbon;David R arkony;Daiqian Xie;Hua Guo
已知圆锥相交会引起非绝热转变，但它们对绝热动力学的影响常常被忽略。以羟甲基自由基的泛音诱导解离为例，证明了基态O-H键断裂受解离路径上电子激发态与基态O-H键沿着的圆锥相交的显著影响，尽管解离态的能量比圆锥相交的能量低得多.除了寿命的差异，几何相位导致不同的H2 CO旋转状态分布相比，使用标准的单态绝热模型，这构成了签名的圆锥形交叉。
Conical intersections are known to cause nonadiabatic transitions, but their effects on adiabatic dynamics are often ignored. Using the overtone-induced dissociation of the hydroxymethyl radical as an example, we demonstrate that ground-state O–H bond rupture is significantly affected by a conical intersection with an electronically excited state along the dissociation path, despite the much lower energy of the dissociating state than that of the conical intersection. In addition to lifetime differences, the geometric phase leads to a different H2CO rotational state distribution compared with that obtained using the standard single-state adiabatic model, which constitutes a signature of the conical intersection.