van der waals interactions in the Cl + HD reaction
The van der Waals forces in the entrance valley of the Cl + HD reaction are shown here to play a decisive role in the reaction's dynamics. Exact quantum mechanical calculations of reactive scattering on a potential energy surface without Cl-HD van der Waals forces predict that the HCl and DCl products will be produced almost equally, whereas the same calculations on a new ab initio potential energy surface with van der Waals forces show a strong preference for the production of DCl. This preference is also seen in crossed molecular beam experiments on the reaction. The study of chemical reaction dynamics has now advanced to the stage where even comparatively weak van der Waals interactions can no longer be neglected in calculations of the potential energy surfaces of chemical reactions.
Skouteris
D
Physical and Theoretical Chemistry Laboratory, South Parks Road, Oxford OX1 3QZ, UK. Institute fur Theoretische Chemie, Universitat Stuttgart, Pfaffenwaldring 55, D-75069 Stuttgart, Germany. Institute of Atomic and Molecular Sciences, Academia Sin.
Manolopoulos
DE
Bian
W
Werner
HJ
Lai
LH
Liu
K