Abstract
The recombinative desorption of D 2 and HD from a Pd(100) surface is studied with rotational state selectivity by resonantly enhanced (vuv + uv) two photon ionisation spectroscopy. For the rotational degree of freedom a strong cooling effect is observed. The first excited vibrational level ( v″ = 1) is much more populated than expected for molecules in thermal equilibrium with the surface. This population increases strongly with the surface temperature. The activation energy for ( v″ = 1) desorption deduced from a Boltzmann plot is less than the vibrational energy of free D 2 and HD molcules.
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