Y. Hurwitz et al., REACTIVITY INDUCED BY COMPLEX-FORMATION - THE REACTION OF O(P-3) WITHHCL DIMERS, The Journal of chemical physics, 106(7), 1997, pp. 2627-2633
The reaction of O(P-3) with HCl . M (M=HCl, Ar) complexes has been stu
died. While the monomer HCl, in its ground vibrational state, reacts e
xtremely slow with O(P-3), it is shown here that the van der Waals com
plexes react with an efficiency of about 3 orders of magnitude larger
than that of the monomer. The reactivity of DCl, on the other hand, is
not enhanced by the complex formation. Molecular dynamics simulation
indicates that the collision complex lifetime increases by several ord
ers of magnitude due to the existence of the ''third body'' in the clu
ster. A model for explaining the complex induced enhancement of reacti
vity is presented and is supported by ab initio calculations. (C) 1997
American Institute of Physics.