Theoretical Study of the Validity of the Polanyi Rules for the Late-Barrier Cl + CHD3 Reaction.
The Polanyi rules, which state that vibrational energy is more efficient in promoting a late-barrier reaction than translational energy, were questioned recently by an experimental unexpected finding that the CH stretch excitation is no more effective in promoting the late-barrier Cl + CHD3 reaction than the translational energy. However, the present quantum dynamics study on the best-available potential energy surface for the title reaction reveals that the CH stretch excitation does promote the reaction significantly, except at low collision energies. Further studies should be carried out to solve the disagreements between theory and experiment on the reaction.
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.|Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Zhaojun
Z
Zhang
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.|Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Yong
Y
Zhou
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.|Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Dong H
DH
Zhang
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.|Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Gábor
G
Czakó
State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.|Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
Joel M
JM
Bowman
mode selectivity; polyatomic reaction; potential energy surface; quantum scattering; reaction dynamics