Diffusion Rates for Hydrogen on Pd(111) from Molecular Quantum Dynamics Calculations

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• 作者：Thiago Firmino ; Roberto Marquardt ; Fabien Gatti ; Wei Dong
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2014
• 出版时间：December 18, 2014
• 年：2014
• 卷：5
• 期：24
• 页码：4270-4274
• 全文大小：268K
• ISSN：1948-7185

文摘

The van Hove formula for the dynamical structure factor (DSF) related to particle scattering at mobile adsorbates is extended to include the relaxation of the adsorbates鈥?vibrational states. The total rate obtained from the DSF is assumed to be the sum of a diffusion and a relaxation rate. A simple kinetic model to support this assumption is presented. To illustrate its potential applicability, the formula is evaluated using wave functions, energies, and lifetimes of vibrational states obtained for H/Pd(111) from first-principle calculations. Results show that quantum effects can be expected to be important even at room temperature.

Keywords:

quantum diffusion; high-dimensional quantum dynamics; heterogeneous catalysis