Photodissociation of HBr/LiF(001): A quantum mechanical model

The photodissociation dynamics of HBr adsorbed on a LiF(001) surface is studied using time-independent quantum mechanics. The photodissociation lineshape and the Br(P(sub 1/2)-2)/Br(P(sub 3/2)-2) yield ratio are computed and compared with the corresponding quantities for gas phase photodissociation. The angular distribution of the hydrogen photofragments following excitation of adsorbed HBr is computed and found to agree qualitatively with experimental data. The effect of polarization of the photon is illustrated and discussed. The field polarization is found to affect significantly the magnitude of the photodissociation signal but not the angular dependence of the photofragment distribution, in agreement with experiment and in accord with expectations for a strongly aligned adsorbed phase

Enhanced Molecular Orientation Induced by Molecular Anti-Alignment

We explore the role of laser induced anti-alignment in enhancing molecular orientation. A field-free enhanced orientation via anti-alignment scheme is presented, which combines a linearly polarized femtosecond laser pulse with a half-cycle pulse. The laser pulse induces transient anti-alignment in the plane orthogonal to the field polarization, while the half-cycle pulse leads to the orientation. We identify two qualitatively different enhancement mechanisms depending on the pulse order, and optimize their effects using classical and quantum models both at zero and non-zero temperature