TRANSITION-STATE DYNAMICS OF CHEMICAL-REACTIONS IN CLUSTERS - A 6-DIMENSIONAL STUDY OF AR(CLHCL)

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.