Reactive scattering of "hot" H atoms with CO2 and OCS

Time-resolved infrared diode laser spectroscopy has been used to state selectively monitor CO produced in the `hot' atom reaction of H with CO2 and OCS. For center of mass (CM) kinetic energies of 2.4 and 1.4 eV, respectively, CO internal excitations are substantially colder than predicted by statistical theory, with energy preferentially channeled into CM translation. In the collision energy regime of these experiments, approximately 10,000 cm-1 above the barrier, statistical rate theory is not applicable even with an intermediate.