Ab. Mccoy, TRANSITION-STATE DYNAMICS OF CHEMICAL-REACTIONS IN CLUSTERS - A 6-DIMENSIONAL STUDY OF AR(CLHCL), The Journal of chemical physics, 103(3), 1995, pp. 986-998
Cluster effects on transition state dynamics are investigated through
a time-dependent calculation of photodetachment spectrum of Ar(ClHCl)(
-). This system is studied by propagating a three-dimensional grid rep
resentation of the wave function in the H atom coordinates, coupled to
three one-dimensional semiclassical Gaussians in the three lowest fre
quency normal coordinates of Ar(ClHCl)(-). Over the 75 fs propagation
times considered here, the motions of the three heavy atoms are very s
mall. Therefore, we expect that the coupled quantum/semiclassical prop
agation will be in quantitative agreement with a full quantum treatmen
t of this system. The couplings between the quantum and semiclassical
degrees of freedom and between the three semiclassical degrees of free
dom are introduced through the time-dependent self-consistent field (T
DSCF) approximation. A computational bottleneck in applying the TDSCF
approximation to such systems is that propagation of each of the modes
requires the;evaluation of the average of the potential over the wave
functions in the three remaining modes. A solution to this problem fo
r H transfer systems is presented and discussed. Comparisons between t
he dynamics of Ar(CMCl) and ClHCl indicate that the presence of the Ar
atom produces a hole in the wave function that is otherwise cylindric
ally symmetric. Possible observable experimental consequences of the i
ntroduction of the Ar atom to this system are discussed. (C) 1995 Amer
ican Institute of Physics.