Six-dimensional quasiclassical and quantum dynamics of H2 dissociation on the c(2 * 2)-Ti/Al(100) surface

The following article appeared in Journal of Chemical Physic 134.11 (2011): 114708 and may be found at http://scitation.aip.org/content/aip/journal/jcp/134/11/10.1063/1.3567397Based on a slab model of H2 dissociation on a c(2 * 2) structure with Ti atoms in the first and third layers of Al(100), a six-dimensional (6D) potential energy surface (PES) has been built. In this PES, a molecular adsorption well with a depth of 0.45 eV is present in front of a barrier of height 0.13 eV. Using this PES, H2 dissociation probabilities are calculated by the classical trajectory (CT), the quasiclassical trajectory (QCT), and the time-dependent wave-packet (TDWP) method. The QCT study shows that trajectories can be trapped by the molecular adsorption well. Higher incident energy can lead to direct H2 dissociation. Vibrational pre-excitation is the most efficient way to promote direct dissociation without trapping. We find that both rotational and vibrational excitation have efficacies close to 1.0 in the entire range of incident energies investigated, which supports the randomization in the initial conditions making the reaction rate solely dependent on the total (internal and translational) energy. The H2 dissociation probabilities from quantum dynamics are in reasonable agreement with the QCT results in the energy range 50-200 meV, except for some fluctuations. However, the TDWP results considerably exceed the QCT results in the energy range 200-850 meV. The CT reaction probabilities are too low compared with the quantum dynamical resultsThe research of J.C.C. is supported by the Marie Curie Research Training Network HYDROGE

Photodissociation of a HCl molecule adsorbed on ice at T=210K

International audienceThis theoretical work concerns the study of the photodissociation of a HCl molecule adsorbed on an ice surface at T = 210 K. Temperature induced disorder is taken into account by a statistics over several configurations extracted from a classical molecular dynamics (MD) simulation. For each configuration, 3D quantum dynamics of the hydrogen photofragment is investigated using the multi-configuration time-dependent Hartree (MCTDH) method. The absorption spectrum at 210 K is obtained by an average over the spectra calculated for each configuration. The surface disorder results in a smoothing of the interferences structures that appear for some given orientations of HCl depending on the surrounding water molecules orientations