화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.104, No.3, 644-651, 2000
Transition state dynamics of Ar-n(ClHCl) (n=0.5): Effects of complex formation on the dynamics and spectroscopy
The effects of intermolecular interactions on the transition state dynamics of the Cl + HCl reaction are investigated through time-dependent quantum simulations of the evolution of the ground state wave function for Ar-n(ClHCl-) on the Ar-n(ClHCl) potential when n = 0-5. A reduced dimensional approach has been employed in which the quantum/semiclassical time-dependent self-consistent field (Q/SC TDSCF) approximation is used to propagate the dynamics of the hydrogen and chlorine atoms, respectively, while the argon atoms are constrained to remain in the equilibrium configuration in Ar-n(ClHCl-). Analysis of the wave functions, obtained from these simulations, shows that as more argon atoms are introduced there is a change in the short time dynamics. When no argon atoms are present, the hydrogen atom rotates off of the Cl-Cl axis. As the number of argon atoms is increased, this motion becomes blocked, and when four or five argon atoms are present, the Cl-H-Cl subsystem is constrained to dissociate collinearly. This change in the dynamics of the hydrogen atom is reflected in an increase in the amount of energy that is transferred to the chlorine atoms asn is increased. It also results in qualitative changes in the calculated photoelectron spectra of Ar-n(ClHCl-).