O(3P)+ CS(X 1Σ+)→CO(X 1Σ+)+ S(3P)反应的产物旋转对准

F. Green, G. Hancock, A. Orr-Ewing
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引用次数: 34

摘要

测量了O(3P)+ CS(X 1Σ+)反应产物CO(X 1Σ+, v′= 14)相对于试剂速度矢量k的旋转取向。用脉冲激光光解NO2生成O(3P)原子,k在实验室框架内排列,用偏振激光诱导荧光检测CO产物。利用先前确定的NO2光解的平移各向异性值,将测量的实验室框架旋转对准值转换为所需的对准参数< P2(J′·k) >值,同时考虑CS自由基的热分布和o原子碎片反冲能量的扩散。J′在12 ~ 35之间,测量了< P2(J′·k) >的值,发现在0±0.25范围内接近于零,平均值略为正。对跃迁的多普勒剖面的测量结果与预测的乘积速度在k方向上的各向同性分布在定性上一致。这些初步结果说明了在实验条件下不涉及使用分子束方法提取散射动力学量子态解析数据的激光方法的范围。
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Product rotational alignment for the reaction O(3P)+ CS(X 1Σ+)→ CO(X 1Σ+)+ S(3P)
Rotational alignment of the CO(X 1Σ+, v′= 14) product of the O(3P)+ CS(X 1Σ+) reaction has been measured relative to the velocity vector k of the reagents. O(3P) atoms were produced with k aligned in the laboratory frame by pulsed laser photolysis of NO2, and the CO product was detected by polarised laser-induced fluorescence. Transformation of the measured laboratory-frame rotational alignments to the required values of the alignment parameter 〈P2(J′·k)〉 were carried out using previously determined values of the translational anisotropy for the photodissociation of NO2, making allowances for both the thermal distribution of CS radicals and the spread of recoil energies of the O-atom fragment. Values of 〈P2(J′·k)〉 were measured for J′ between 12 and 35, and found to be close to zero to within the range 0 ± 0.25, with the mean value being slightly positive. Measurements of the Doppler profiles of the transitions are in qualitative agreement with those predicted for an isotropic distribution of product velocities about the k direction. These preliminary results illustrate the scope of laser based methods of extracting quantum-state-resolved data on scattering dynamics under experimental conditions which do not involve the use of molecular beam methods.
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Solvation. List of Posters Energy and structure of the transition states in the reaction OH + CO → H + CO2 Transition-state control of product rotational distributions in H + RH → H2+ R reactions (RH = HCl, HBr, HI, CH4, C2H6, C3H8) Quantum-dynamical characterization of reactive transition states
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