Department of Chemistry and Molecular Biology, North Dakota State University, Fargo, North Dakota 58108, USA.
J Phys Chem A. 2010 Apr 1;114(12):4304-12. doi: 10.1021/jp9072679.
The dynamics of four-centered HCl elimination from chloroethane are studied using a mixed quantum-classical method based on a reaction path Hamiltonian. Both the structural details of the reaction and the partitioning of the exit-channel potential energy to the products are analyzed. The minimum energy path was calculated at the B3LYP/6-311++G(2d,2p) level of theory, which was followed by energy-partitioning dynamics computations. Selective vibrational excitation of the HCl product was observed, leading to a vibrational state distribution in good agreement with experiment. Differences between HCl elimination from C(2)H(5)Cl and HF elimination from C(2)H(5)F, particularly in the ethylene fragment, were observed and are discussed.
用基于反应路径哈密顿量的量子-经典混合方法研究了氯乙烷中四中心 HCl 消除的动力学。分析了反应的结构细节和出口通道势能在产物中的分配。在 B3LYP/6-311++G(2d,2p)理论水平上计算了最低能量路径，然后进行了能量分配动力学计算。观察到 HCl 产物的选择性振动激发，导致与实验很好吻合的振动状态分布。观察到 C(2)H(5)Cl 中 HCl 的消除与 C(2)H(5)F 中 HF 的消除之间的差异，特别是在乙烯片段中，并进行了讨论。
