Vibrational state dependence of D2 dissociation on Ag(111)

Abstract

Initial sticking probabilities for D2 dissociative chemisorption at a Ag(111) surface have been measured for translational energies in the range Ei=220–500 meV, as a function of incident angle θi and gas temperature, using seeded molecular beams. Sticking probabilities are dependent on the D2 internal state distribution and scale with the normal component of the translational energy. The data has been fit by assuming that dissociation is independent of molecular rotation, being the sum of contributions from molecules in different vibrational states v with a sticking function S0(Ei,θi,v)=A/2{1+tanh[Ei cos2 θi−E0(v)]/w(v)}, in a manner similar to the behavior on copper. Sticking parameters E0, the translational energy required for S0 to reach half of its maximum value, are determined with good precision (±25 meV) for levels v=3 (328 meV) and v=4 (170 meV) with width parameters w=54 and 63 meV, respectively, while the barriers for levels v=1 and 2 are close to the upper limit of the sticking data and E0 is estimated as 700±100 and 510±70 meV, respectively. Parameters for the vibrational ground state (v=0) could not be obtained, since sticking of this state is negligible at translational energies less than 500 meV. No dissociation could be observed at thermal energies Ei⩽70 meV either on a flat or a defective surface.