Tsai Ming-Tsang, Tsai Po-Yu, Alexander Millard H, Lin King-Chuen
Department of Chemistry, National Taiwan University, Taipei 106 and Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 106, Taiwan.
Chemphyschem. 2008 Mar 14;9(4):572-8. doi: 10.1002/cphc.200700779.
An experimental and theoretical investigation of rotational energy transfers (RET) of CH involving the B (2)Sigma(-) (v=0, 0</=N</=5, F) state by collisions with Ar is undertaken, using the photolysis-probe technique. Time-resolved laser-induced fluorescence resulting from an initially prepared fine-structure label is dispersed using a step-scan Fourier transform spectrometer. The spin-resolved RET rate constants are evaluated with the simulation of a kinetic model. The quantum-scattering method is used for the calculation of the fine-structure-resolved cross sections and rate constants in the rotationally inelastic collisions. The theoretical values are generally consistent with our experimental findings, both in the order of magnitude and trend of N and DeltaN dependence. The propensity rules obtained from the experiments are essentially obeyed by theoretical calculations, and are also in accordance with those reported by Kind and Stuhl. The RET rate constants obtained for the v=0 level are smaller than those obtained previously for v=1. The discrepancy in the RET behavior may be caused by an anisotropy difference of the interaction potential resulting from vibrational excitation.
利用光解探测技术，对CH与Ar碰撞涉及B(2)Σ⁻(v = 0, 0≤N≤5, F)态的转动能量转移(RET)进行了实验和理论研究。由初始制备的精细结构标记产生的时间分辨激光诱导荧光，使用步进扫描傅里叶变换光谱仪进行色散。通过动力学模型的模拟评估自旋分辨的RET速率常数。量子散射方法用于计算转动非弹性碰撞中精细结构分辨的截面和速率常数。理论值在数量级以及N和ΔN依赖性趋势上通常与我们的实验结果一致。从实验中获得的倾向规则在理论计算中基本得到遵守，并且也与Kind和Stuhl报道的一致。v = 0能级获得的RET速率常数小于先前v = 1时获得的速率常数。RET行为的差异可能是由振动激发导致的相互作用势的各向异性差异引起的。
