TRANSITION-STATE DYNAMICS OF X-DEPENDENT SELF-CONSISTENT-FIELD APPROXIMATION(HX REACTIONS USING THE TIME)

It has been demonstrated that the time-dependent self-consistent field approximation (TDSCF) provides an excellent approach for studying the three-dimensional quantum dynamics of ClHCl (J = 0) starting from the transition state (McCoy, A. B. et al. 1994, J. chem. Phys., 101, 1975 ). The question is now explored of whether this result is a consequenc e of the large difference between the masses of the Cl and H atoms or a fundamental property of the approximation. The quality of the result s of TDSCF propagations on ClHCl is compared with that for a system in which the mass of Cl is reduced to equal that of deuterium. The light er mass of the Cl atoms in the second system means that the wavefuncti on should be less well approximated by a product form than it was for ClHCl. This approximate separability of the wavefunction is the basis of TDSCF propagations. Therefore, over the 36 fs propagation times con sidered here, the TDSCF wavefunction for the system containing the lig ht Cl atoms is not as accurate as that for ClHCl. Nevertheless, observ able properties predicted by TDSCF propagations are in good agreement with those of numerically exact propagations for both systems.