Angular dependence of rotational and vibrational energies of product CO2 in CO oxidation on Pd(110)

The rotational and vibrational energies of product CO(2) in the CO oxidation on Pd(110) surfaces were measured as functions of desorption angles. The antisymmetric vibrational temperature (T(a)) was separately determined from the other vibrational modes from the normalized chemiluminescence intensity. The rotational temperature (T(rot)) and vibrational temperature averaged over the symmetric and bending modes (T(sb)) were then determined by the position and width of spectra by comparison with simulated spectra. On Pd(110)-(1x1), with increases in the desorption angle, T(a), T(sb) and T(rot) decreased in the [001] direction but remained constant in [11[combining macron]0]. However, such anisotropy disappeared when the ratio of exposure of O(2) to that of CO decreased, resulting in a gradual decrease of the three temperatures with increases in the desorption angle. On Pd(110) with missing rows, the three temperatures increased in [001] but decreased in [11[combining macron]0], indicating that the transition state changes with the geometry of the substrate. On Pd(110) with missing rows, T(a) was significantly lower than T(sb), although T(a) was close to or higher than T(sb) on Pd(110)-(1x1). However, there was no significant difference in the angular dependence between T(a), T(sb) and T(rot).