Sticking Probability and Reactivity of Hyperthermal O2 Molecules Impinging on CO Pre-covered Pd(100): Effect of Rotational States with K > 1

Collisional alignment in the supersonic expansion of oxygen seeded in lighter carriers allows to produce rotationally aligned beams which were used to study the sticking probability, S, and the reactivity, , of helicoptering and cartwheeling O-2 in the lowest rotational state impinging normally onto Pd(100). Molecules with different rotational alignment are thereby chosen by mechanically selecting either the slow or the fast speed tail of the beam velocity distribution. Here we show for O-2 reacting with CO pre-covered Pd(100) that even a moderate increase in the nozzle temperature, T-N, with respect to room temperature implies significant changes in both S and . Since T-N affects mainly the rotational state distribution in the formed beam, we conclude that molecules in rotational states with K a parts per thousand yen 3 behave very differently from those with K = 1. Data are presented for both small and intermediate CO pre-coverage.