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OCS分子在里德堡F态的真空紫外光解动力学:S(^3P_\rmJ=2,1,0)产物通道

Vacuum Ultraviolet Photodissociation Dynamics of OCS via the F Rydberg State: the S(^3P_\rmJ=2,1,0) Product Channels

  • 摘要: 本文利用可调谐真空紫外光源和时间切片离子速度成像技术研究了OCS分子的真空紫外光解动力学. 在对应OCS里德堡F态的五个光解波长下(133.26 nm\sim139.96 nm)实验采集了S(^3P_J=2, 1, 0)产物的离子影像,从中发现了两个解离通道:S(^3P_J=2, 1, 0)+CO(X^1\Sigma^+)和S(^3P_J=2, 1, 0)+CO(A^3\Pi),其中前者为主要通道. 离子影像中CO产物的振动结构可部分分辨. 从离子影像中提取出了S(^3P_J=2, 1, 0)+CO(X^1\Sigma^+)通道的产物总平动能分布、各向异性参数和CO振动态分支比等信息. 发现了对应OCS在F态的几个低振动态下光解的产物各向异性参数取负值,而对应F态的几个高振动态下光解产物的各向异性参数为正值. 另外,同一光解波长下三种S产物S(^3P_2)、S(^3P_1)和S(^3P_0)的各向异性参数也不相同. 经分析,这些现象可能来源于激发区域的其它不同对称性的电子态的贡献,从而导致解离过程中同时存在平行解离和垂直解离. 本工作有利于进一步理解OCS真空紫外光解中的非绝热耦合作用.

     

    Abstract: Vacuum ultraviolet (VUV) photodissociation dynamics of carbonyl sulfide was investigated experimentally by using a tunable photolysis light source and the time-sliced velocity map ion imaging technique. Ion images of S(^3P_J=2, 1, 0) dissociation products were measured at five photolysis wavelengths from 133.26 nm to 139.96 nm, corresponding to the F Rydberg state of OCS. Two dissociation channels: S(^3P_J)+CO(X^1\Sigma^+) and S(^3P_J)+CO(A^3\Pi) were observed with the former being dominant. The vibrational states of CO co-products were partially resolved in the ion images. The product total kinetic energy releases, anisotropy parameters (\beta), and the branching ratios of high-lying CO vibrational states were determined for the S(^3P_J)+CO(X^1\Sigma^+) channel. We found that the anisotropy parameters suddenly changed from negative to positive when OCS was excited to the higher vibrational levels of the F state. Furthermore, the anisotropy parameters for S(^3P_J) products of J=2, 1, 0 were even different. These anomalous phenomena may result from the simultaneous existence of both parallel and perpendicular dissociation mechanisms, suggesting the involvement of other electronic states with different symmetry in the initially-excited energy region. This work provides a further understanding of the nonadiabatic couplings in the VUV photodissociation process of OCS.

     

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