REACTIVITY INDUCED BY COMPLEX-FORMATION - THE REACTION OF O(P-3) WITHHCL DIMERS

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.