Ab. Mccoy et al., REACTIONS OF OXYGEN-ATOMS WITH VAN-DER-WAALS COMPLEXES - THE EFFECT OF COMPLEX-FORMATION ON THE INTERNAL ENERGY-DISTRIBUTION IN THE PRODUCTS, The Journal of chemical physics, 108(23), 1998, pp. 9651-9657
Reactions of atomic oxygen with complexes containing HCl are investiga
ted and the OH product state distributions are compared to those obser
ved for the corresponding reactions of HCl monomers. In previous studi
es of reactions of O(P-3) with HCl and hydrocarbon complexes, rotation
ally colder OH product state distributions were observed, when compare
d to the corresponding reactions of monomers. In contrast, we find tha
t reactions of O(D-1) with HCl clusters yield OH rotational distributi
ons that are unaffected by the incorporation of HCl into a van der Waa
ls complex. Quasiclassical trajectories are run on collisions of oxyge
n with HCl and Ar ... HCl at 1 eV collision energies to investigate th
e differences in the dynamics of the O(D-1) and O(P-3) reactions. It i
s found that when the van der Waals complex is longer lived than the c
ollision complex, rotational and vibrational cooling are observed. In
contrast, when the dissociation of the van der Waals complex is prompt
; compared to the collision complex lifetime, the effects of complex f
ormation on the internal energy of the OH product become negligible. (
C) 1998 American Institute of Physics.