ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
State resolved characterization of nascent gas phase products is used as probe for the dynamics of an energetic surface reaction. This is achieved in the photodissociation of monolayer phosgene adsorbed on Ag(110). Irradiation of adsorbed Cl2CO in a broad photon energy range (hν=1.9–6.4 eV) leads to dissociation, with Cl retained on the surface and CO desorbing into the gas phase. The translational energy of product CO (g), 〈Etrans〉=0.26 eV, is independent of hν, even at the threshold photon energy (1.9 eV). This result establishes a dissociative electron attachment mechanism involving a reactive intermediate, ClCO, whose prompt dissociation serves as a probe to surface dissociation dynamics. Consistent with translation, internal state distribution of product CO (g) also shows an energetic origin: The rotational distribution, with an overall flux-weighted mean rotational energy of 〈Erot〉=0.17 eV, can be approximated by a bimodal Boltzmann distribution with rotational temperatures of 700 K at low J(s) and 7000 K at high J(s); the relative vibrational population is Nν=1/Nν=0=0.30. Contrary to common expectation based on quenching rates, both translational and rotational energies of CO (g) from monolayer photodissociation are much higher than those from the direct photodissociation in multilayers. This is taken as evidence for concerted reaction dynamics on the surface: The high exothermicity in the Cl–Ag bond formation on the surface exerts part of the energy to the Cl–CO coordinate, leading to higher energies in CO (g). © 1996 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.471237
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