Nonintuitive Asymmetry in the Three-Body Photodissociation of CH3COCN
Nonintuitive Asymmetry in the Three-Body Photodissociation of CH3COCN
复制标题
CH3COCN 三体光解离中的非直观不对称性
DOI：
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发表时间：
1997
期刊：
影响因子：
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通讯作者：
G. Hall
中科院分区：
文献类型：
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作者：
S. North;A. J. Marr;A. Furlan;G. Hall
使用高分辨率瞬态调频 (FM) 光谱和光碎片平移光谱研究了乙酰氰化物 (CH3COCN) 193 nm 光解的路径、能量学和机制。 FM 光谱测量的 CN 碎片的振动和旋转状态分布与之前的工作非常一致。 CN 的量子产率为 0.9 ± 0.2。状态相关的平移能量分布是非统计的。 CN 碎片的速度和角动量的实验室框架各向异性非常小，但观察到显着的 v·j 相关性，表明 CN 角动量倾向于垂直于反冲速度。光碎片平移光谱提供了动能分布和碎片路径的独立确认。尽管存在很大差异，但综合测量结果与对初级 CN 消除优于 CH3 消除的强烈偏好一致。
Pathways, energetics, and mechanisms of the 193 nm photodissociation of acetyl cyanide (CH3COCN) have been investigated using high-resolution transient frequency modulation (FM) spectroscopy and photofragment translational spectroscopy. Vibrational and rotational state distributions of CN fragments measured by FM spectroscopy are in good agreement with previous work. The quantum yield of CN is found to be 0.9 ± 0.2. State-dependent translational energy distributions are nonstatistical. The laboratory-frame anisotropy of both velocity and angular momentum of CN fragments is vanishingly small, yet significant v·j correlations are observed, indicating a preference for the CN angular momentum to be perpendicular to the recoil velocity. Photofragment translational spectroscopy provided independent confirmation of kinetic energy distributions and fragmentation pathways. The combined measurements are consistent with the strong preference for primary CN elimination over CH3 elimination, despite a large difference...