Kinetics and dynamics of the radical complex mechanism: Application to the ClO+ClO recombination reaction

PHYS 458

Jingyao Liu,, Department of Atmospheric, Oceanic, and Space Sciences, University of Michigan, 2455 Hayward, Space Research Building, Ann Arbor, MI 48109-2143 and John R Barker,, Department of Atmospheric, Oceanic, and Space Sciences & Chemistry Department, University of Michigan, 2455 Hayward, 1520 Space Research Building, Ann Arbor, MI 48109-2143.
The radical complex (or chaperon) mechanism for recombination reactions is thought to be more important for small species than the conventional energy transfer mechanism, especially at low temperatures. We develop a model potential energy surface (PES) and use it with quasi-classical trajectory calculations to investigate the nascent energy distributions of ClOOCl* produced via the ClO+ClO•N2 reaction. The geometries and frequencies of the stationary points on the PES are optimized at the B3LYP/6-311+G(3df) level of theory, and the energies are refined at the CCSD(T)/6-311+G(3df) (single-point) level. The nascent energy distributions control the product distributions, including the minor channels. By initializing RRKM-master equation simulations using the energy distribution of ClOOCl*, we can calculate subsequent product yields of ClOOCl, Cl2+O2 and Cl+ClO2 that result from the chaperon mechanism. We will discuss how the van der Waals well depth affects the yields, compared to the conventional energy transfer mechanism.

Poster Session
7:30 PM-10:00 PM, Wednesday, 13 September 2006 Moscone Center -- Hall D, Poster

Division of Physical Chemistry

The 232nd ACS National Meeting, San Francisco, CA, September 10-14, 2006