Rotational transitions and diffraction in D2 scattering from the LiF(001) surface: theory and experiment.

High probabilities of energy transfer from translation to molecular rotations are observed in the scattering of n-D(2) from LiF(001) at an incident beam energy of 85.3 meV. For the 100 incidence direction, close-coupling calculations yield ratios of the rotationally inelastic (j=0-->2) and (j=1-->3) peaks to the rotationally elastic specular peaks (G=0) that are in reasonable agreement with experiment, as are the ratios of the rotationally elastic diffraction peak intensities to the specular peak intensities. The agreement between theory and experiment is also quite good for the rotationally inelastic diffractive (-1-1) transitions for (j=1-->3), but rather poor for (j=0-->2). The calculations show that the interaction between the electrostatic field of the surface ions and the quadrupole moment of the D(2) molecule efficiently promotes the (j=0-->2) and (j=1-->3) transitions. If this electrostatic interaction is excluded from the potential model, the ratios of the (j=0-->2) and (j=1-->3) rotationally inelastic peaks to the corresponding specular peaks show a large discrepancy with experiment, underlining the importance of this interaction. The close-coupling calculations show a somewhat worse agreement with experiment for the 110 incidence direction. In particular, the sharp peaks observed experimentally in the ratios of the peak intensities of the rotationally inelastic G=0 (j=0-->2) and (j=1-->3) to the rotationally elastic G=0 transitions as a function of incident angle are not reproduced by the calculations. The theoretical ratios of the peak intensities of the rotationally elastic diffraction to G=0 transitions are shifted to lower incidence angles with respect to experiment. The rotationally inelastic diffractive (-10) transitions present an interesting resonance phenomenon for the (j=0-->2) rotational transition. This resonance is predicted by both theory and experiment, although at rather different incident angles.