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

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 consequence of the large difference between the masses of the Cl and H atoms or a fundamental property of the approximation. The quality of the results 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 lighter mass of the Cl atoms in the second system means that the wavefunction 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 considered here, the TDSCF wavefunction for the system containing the light Cl atoms is not as accurate as that for ClHCl. Nevertheless, observable properties predicted by TDSCF propagations are in good agreement with those of numerically exact propagations for both systems.