Cl + CHD3（v1 = 1）反应的振动增强因子：转动探针效应

Vibrational Enhancement Factor of the Cl + CHD3(v1 = 1) Reaction: Rotational-Probe Effects.

作者信息

Wang Fengyan, Lin Jui-San, Cheng Yuan, Liu Kopin

机构信息

†Institute of Atomic and Molecular Sciences (IAMS), Academia Sinica, P.O. Box 23-166, Taipei, Taiwan 10617.

‡Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan.

出版信息

J Phys Chem Lett. 2013 Jan 17;4(2):323-7. doi: 10.1021/jz302017e. Epub 2013 Jan 7.

DOI:10.1021/jz302017e

PMID:26283442

Abstract

The vibrational enhancement factor in the Cl + CHD3(v1 = 1) reaction is revisited over the collisional energy range of 2-5.9 kcal mol(-1). Contrary to the previous results obtained by probing the low-|N, K⟩ states of CD3(v = 0) products, CH stretching excitation becomes more efficacious than the same amount of translational energy in promoting the HCl(v) + CD3(v = 0) product pairs when all-|N, K⟩ states are probed. Whereas the new vibrational enhancement factors, which are three to four times larger than the previous report, agree reasonably well with a recent reduced-dimensionality quantum dynamics calculation, a cautious note is made on the different initial |J,K⟩ rotational selections of the CHD3 reactants in the present theory-experiment comparison.

摘要

在2 - 5.9千卡摩尔⁻¹的碰撞能量范围内，重新研究了Cl + CHD₃（v₁ = 1）反应中的振动增强因子。与之前通过探测CD₃（v = 0）产物的低|N, K⟩态获得的结果相反，当探测所有|N, K⟩态时，在促进HCl（v）+ CD₃（v = 0）产物对方面，CH拉伸激发比相同数量的平动能更有效。新的振动增强因子比之前的报告大两到三倍，与最近的降维量子动力学计算结果相当吻合，但在当前理论 - 实验比较中，对CHD₃反应物不同的初始|J, K⟩转动选择需谨慎对待。