Ion-pair dissociation dynamics of Cl2: adiabatic state correlation.
Ion-pair dissociation dynamics of Cl2: adiabatic state correlation.
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Cl2 的离子对解离动力学：绝热态相关性。
DOI：
10.1021/jp804272w
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发表时间：
2008
期刊：
影响因子：
--
通讯作者：
Y. Mo
中科院分区：
文献类型：
--
作者：
Chang Zhou;Y. Hao;Y. Mo
采用相干极紫外（XUV）辐射和速度图成像）方法研究了 12.41-12.74 eV 范围内 Cl2 -->(XUV) Cl(-)((1)S0) + Cl(+)((3P(2,1,0)) 的离子对解离动力学。测量了离子对产额谱，并记录了谱中峰的 72 个 Cl(-)((1)S0) 速度图图像。从图像中，确定了三个自旋轨道分量Cl(+)((3)P2)、Cl(+)((3)P1)和Cl(+)((3)P0)之间的分支比及其相应的各向异性参数β。离子对解离机制可以通过里德堡态预解离到离子核 Cl2(+)(A(2)Pi(u)) 来解释。 Cl(-)((1)S0) 离子对产额谱是根据成像实验中确定的里德堡态的对称特性指定的。平行和垂直跃迁分别对应于两个主要里德伯级数的激发，[A(2)Pi(u)]3d pi(g)、(1)Sigma(u)(+) 和 [A(2)Pi(u)]5s sigma(g)、(1)Pi(u)。对于Cl(+)((3)P0)的产生，发现它们全部来自平行跃迁。但对于Cl(+)((3)P1)，大部分来自垂直跃迁。 Cl(+)((3)P2)的产生是该能区的主要通道，它们来自平行跃迁和垂直跃迁。研究发现，对于大多数预解离，总电子角动量在分子轴 (Ω) 上的投影是守恒的。离子对解离可以被视为里德堡态对称性质的探针。
The ion-pair dissociation dynamics of Cl2 -->(XUV) Cl(-)((1)S0) + Cl(+)((3P(2,1,0)) in the range 12.41-12.74 eV have been studied employing coherent extreme ultraviolet (XUV) radiation and the velocity map imaging) method. The ion-pair yield spectrum has been measured, and 72 velocity map images of Cl(-)((1)S0) have been recorded for the peaks in the spectrum. From the images, the branching ratios among the three spin-orbit components Cl(+)((3)P2), Cl(+)((3)P1) and Cl(+)((3)P0) and their corresponding anisotropic parameters beta have been determined. The ion-pair dissociation mechanism is explained by predissociation of Rydberg states converging to ion-core Cl2(+)(A(2)Pi(u)). The Cl(-)((1)S0) ion-pair yield spectrum has been assigned based on the symmetric properties of Rydberg states determined in the imaging experiments. The parallel and perpendicular transitions correspond to the excitation to two major Rydberg series, [A(2)Pi(u)]3d pi(g), (1)Sigma(u)(+) and [A(2)Pi(u)]5s sigma(g), (1)Pi(u), respectively. For the production of Cl(+)((3)P0), it is found that all of them are from parallel transitions. But for Cl(+)((3)P1), most of them are from perpendicular transitions. The production of Cl(+)((3)P2) is the major channel in this energy region, and they come from both parallel and perpendicular transitions. It is found that for most of the predissociations the projection of the total electronic angular momentum on the molecular axis (Omega) is conserved. The ion-pair dissociation may be regarded as a probe for the symmetric properties of Rydberg states.