We have performed detailed semiclassical stochastic trajectory, classical trajectory and exact quantal calculations on H 2 and D 2 collisions with Cu(100) using two different interaction potentials. The first is weakly anisotropic while the second is as anisotropic as possible without violating the free rotational motion of H 2 at the equilibrium distance for physisorption. Energy transfer to phonons was modelled within the semiclassical stochastic trajectory method using the generalized Langevin equation approach. Energy transfer to electron-hole pairs was incorporated via an electronic friction coefficient, using two different parametrized forms, one of which gives strong friction and the other weak. Our results can be summarized as follows for the Cu(100) system: (1) Even for the very anisotropic potential, trapping via translational to rotational energy conversion does not occur to any significant degree. (2) The dependence of the sticking coefficient on the rotational level, j, is negligible for both potentials, irrespective of whether energy is transferred to phonons and/or electron-hole pairs. (3) The sticking coefficient depends strongly upon the orientation state, m, of the rotor for the strongly anisotropic potential. (4) The magnitude of the sticking coefficient varies from 0.03–0.1 for H 2Cu and 0.06–0.11 for D 2Cu, with the lower numbers appropriate for the phonon mechanism and the upper for both phonons and (strong coupling to) electron-hole pairs. (5) The ratio of sticking coefficients for D 2 and H 2 is ≈1.8 for phonon dissipation and ≈1.0 for both phonon and (strong coupling to) electron-hole pair dissipation. Fewer results for the H 2Ag(111) system are reported but these are in qualitative accord with the H 2Cu(100) features. The magnitude of the sticking coefficient is smaller for H 2Ag than for H 2Cu.
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