期刊
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
卷 107, 期 49, 页码 20881-20886出版社
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1001098107
关键词
Born-Oppenheimer approximation; dissociative chemisorption; molecule-surface scattering
资金
- Stichting Nationale Computerfaciliteiten
- subdivision Chemische Wetenschappen of the Nederlandse Organisatie voor Wetenschappelijk Onderzoek
- Ministerio de Ciencia e Innovacion (Spain)
- Direccion General de Investigacion [N FIS2007-60064]
The accuracy of dynamical models for reactive scattering of molecular hydrogen, H(2), from metal surfaces is relevant to the validation of first principles electronic structure methods for molecules interacting with metal surfaces. The ability to validate such methods is important to progress in modeling heterogeneous catalysis. Here, we study vibrational excitation of H(2) on Cu(111) using the Born-Oppenheimer static surface model. The potential energy surface (PES) used was validated previously by calculations that reproduced experimental data on reaction and rotationally inelastic scattering in this system with chemical accuracy to within errors <= 1 kcal/mol approximate to 4.2 kJ/mol [D az C, et al. (2009) Science 326: 832-834]. Using the same PES and model, our dynamics calculations underestimate the contribution of vibrational excitation to previously measured time-of-flight spectra of H(2) scattered from Cu(111) by a factor 3. Given the accuracy of the PES for the experiments for which the Born-Oppenheimer static surface model is expected to hold, we argue that modeling the effect of the surface degrees of freedom will be necessary to describe vibrational excitation with similar high accuracy.
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