Transition state dynamics of Ar(n).(IHI) (n = 0-20)

Classical trajectory simulations of the dynamics of Ar(n).(IHI) with n = 0-20 are performed to investigate the effects of solvation on the transition state dynamics of the I + HI reaction. Initial conditions for the classical trajectories are sampled from the quantum ground-state phase space distribution for Ar(n).(IHI)-, given by the Wigner distribution function. Neumark and co-workers recently reported a shift of the Ar(n).(IHI)- photoelectron spectra to lower electron kinetic energies when the number of argon atoms was increased from 0 to 15. Analogous shifts are found in the present calculations, and excellent agreement between the experimental and calculated shifts is found. Longer lifetimes of the IHI complex and increasing energy transfer between the hydrogen atom and the argon and iodine atoms are also observed as the number of argon atoms is increased.