State-Selective Studies of T→R, V Energy Transfer: The H+CO System

Collisional energy transfer from H atoms to CO(v=0, J≈2) has been studied at a collision energy of 1.58±0.07 eV by photolyzing H2S at 222 nm in a nozzle expansion with CO and probing the CO(v , J ) levels using tunable VUV laser-induced fluorescence. The ratio CO(v =1)/CO(v =0) is found to be 0.1±0.008. The rotational distribution of CO(v =0) peaks at J gradually; population is still observed at J \u3e45. The rotational distribution of CO(v =1) is broad and peaks near J =20. The experimental results are compared to quasiclassical trajectory calculations performed both on the H+CO surface of Bowman, Bittman, and Harding (BBH) and on the surface of Murrell and Rodriguez (MR). The experimental rotational distributions, particularly those for CO(v =1), show that the BBH surface is a better model than the MR surface. The most significant difference between the two surfaces appears to be that for energetically accessible regions of configuration space the derivative of the potential with respect to the CO distance is appreciable only in the HCO valley for the BBH surface, but is large for all H atom approaches in the MR potential. Because the H-CO geometry is bent in this valley, vibrational excitation on the BBH surface is accompanied by appreciable rotational excitation, as observed experimentally