Mixed quantum-classical reaction path dynamics of HCl elimination from chloroethane.
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.
Bladow
Landon L
LL
Department of Chemistry and Molecular Biology, North Dakota State University, Fargo, North Dakota 58108, USA. landon.bladow@ndsu.edu
Stopera
Christopher J
CJ
Thweatt
W David
WD
Page
Michael
M