Recombinative desorption of H2 and D2 from Cu(110) and Cu(111): Determination of nonequilibrium rovibrational distributions

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Abstract
Rotational and vibrational state distributions have been determined for H2 and D2 recombinatively desorbing from clean Cu(110) and Cu(111) surfaces in ultra‐high vacuum. A 2+1 resonance‐enhanced multiphoton ionization technique is employed. Rotational distributions for both isotopes are found to be mildly non‐Boltzmann and having mean rotational energies less than the surface temperature Ts and equal for both surfaces. The (v″=1)/(v″=0) vibrational population ratio for both H2 and D2, however, is ∼50 times greater than the value expected for an equilibrium ensemble at Ts for desorption from Cu(110) and ∼100 times greater from Cu(111).