Ab. Mccoy, TRANSITION-STATE DYNAMICS OF X-DEPENDENT SELF-CONSISTENT-FIELD APPROXIMATION(HX REACTIONS USING THE TIME), Molecular physics, 85(5), 1995, pp. 965-979
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.