K. Someda et H. Nakamura, DECOUPLING SURFACE-ANALYSIS OF CL+CL2 REACTION EMBEDDED IN AR52 CLUSTER, Bulletin of the Chemical Society of Japan, 67(10), 1994, pp. 2659-2664
A model triatomic reaction Cl+Cl2-->Cl2+Cl embedded in an Ar52 van der
Waals cluster is analyzed classical mechanically by a novel theoretic
al method called ''decoupling surface analysis''. This method generate
s new reactive and vibrational variables in which the kinetic coupling
as well as the potential coupling are minimized. An analysis of local
frequencies of the vibrational variables along the reaction coordinat
e clarifies how the motions of ambient Ar atoms are coupled with the c
entral Cl3 system. When the local frequencies are plotted as a functio
n of the reaction coordinate, avoided crossings among these curves are
observed. Mixing of Cl motion and Ar motion is clearly detected by th
ese avoided crossings. The vibrational mode having a character of the
symmetric stretch of Cl3 shows exclusively strong coupling with the re
active motion. This mode, however, very weakly couples with the ambien
t Ar motion. On the other hand, the bending and translation of Cl3 are
strongly mixed with the motions of ambient Ar atoms and produce unsta
ble modes, which play the most significant role in energy exchange bet
ween the central reaction system and the ambient Ar atoms.