Multiconfiguration time-dependent Hartree method applied to molecular dissociation on surfaces: H2 + Pt(111).
Four-dimensional quantum dynamics calculations are performed on the dissociative chemisorption of H(2) on Pt(111) using the multiconfiguration time-dependent Hartree method. The aim of this work is to study the performance of the multiconfiguration time-dependent Hartree method for a gas-surface reaction by comparison with the standard time-dependent wave-packet propagation method. The initial-state resolved dissociation probability of H(2) is calculated within two four-dimensional models. The first four-dimensional model treats explicitly the rotational motion of the molecule and the H(2) dissociation is studied above two different sites of the Pt(111). For this model, only a potential-energy surface of general form was available. This potential was refitted to a sum of product form to allow efficient calculations with the multiconfiguration time-dependent Hartree method. The second model focuses on the description of the center-of-mass motion parallel to the surface, the rotational motion of the molecule being frozen. These four-dimensional quantum dynamics calculations yield important insights which can help with performing full six-dimensional calculations on H(2) dissociating on Pt(111). The multiconfiguration time-dependent Hartree method is shown to be particularly efficient for computing initial-state selective dissociation probabilities for the system studied, with a good accuracy and a reduced amount of memory and computational time when compared to the standard time-dependent wave-packet method.
Laboratoire de Physico-Chimie Moléculaire, UMR 5803 CNRS, Université Bordeaux 1, 351 Course de la Liberation, Talence, France. c.crespos@lpcm.u-bordeaux1.fr
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