Abstract

Distributions of internal states and kinetic energies are reported for the laser-induced desorption of NO from a platinum foil. Two desorption channels are observed, one with internal-state populations which are well fit by Boltzmann distribution functions that correspond to the peak surface temperature. The second desorption channel displays population distributions which are non-Boltzmann: kinetic energies exceed the peak surface temperature by a factor of ≈5; kinetic energies depend on J; the spin–orbit states are inverted; and the vibrational population exceeds that associated with the maximum surface temperature by a factor of 50. The wavelength dependence of the non-Boltzmann desorption signal suggests that a substrate mediated desorption process is operative.

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