Effects of reactant internal excitation and orientation on dissociative chemisorption of H2O on Cu(111): Quasi-seven-dimensional quantum dynamics on a refined potential energy surface

Abstract

To understand the influence of reactant internal excitation and orientation on the dissociative chemisorption of water on Cu(111), a quasi-seven-dimensional quantum dynamics study has been carried out on a refined potential energy surface (PES). The new PES was modified in the asymptotic region to allow an accurate characterization of the H(2)O ro-vibrational levels. The mode selectivity of the reaction was reexamined on the new PES and found to be consistent with our earlier work. To rationalize the observed mode selectivity, a vibrationally adiabatic reaction path model was determined on this PES. Furthermore, the reactivity for various rotationally excited H(2)O was investigated. It is shown that even low rotational excitation in H(2)O can either enhance or inhibit the reaction and the reactivity depends on the orientation of the impinging molecule.

Dynamics of Water Dissociative Chemisorption on Ni(111): Effects of Impact Sites and Incident Angles

“…QCT calculations confirmed the mode specificity in the dissociative chemisorption of D 2 O observed in a recent experiment [16] and validated our reduced-dimensional model. [16,19,20] These results also uncovered the influence of the reaction path topography at different impact sites and substantial roles played by translational energy both parallel and perpendicular to the surface.…”

Six-dimensional quantum dynamics study for the dissociative adsorption of HCl on Au(111) surface

“…zhangdh@dicp.ac.cn six-dimensional quantum dynamics calculations of H 2 O on Cu(111) [37][38][39] and eight-dimensional calculations of CH 4 on Ni(111). 40 Accurate PESs were fit by the permutationally invariant polynomial approach of Bowman and co-workers 41,42 based on energy points from density functional theory (DFT) calculations.…”

An improved Lobatto discrete variable representation by a phase optimisation and variable mapping method

“…In recent years, developing efficient numerical methods for the solution of the Schrödinger equation arose much interest. However, due to the numerical complications, many practical problems, such as the description of multi-dimensional systems [17] and long-range interactions [18,19], still are very demanding for theoretical calculations following quantum mechanics principles.…”

“…Efficient numerical methods for solving the Schrödinger equation are important for understanding a wide variety of physical and chemical processes, such as photodissociation [1,2], photo-absorption spectra [3][4][5][6][7], pre-dissociation [8], resonance Raman spectra [9,10], reactive scattering [11][12][13] and molecule-surface scattering [14][15][16][17]. In recent years, developing efficient numerical methods for the solution of the Schrödinger equation arose much interest.…”