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Journal of Chemical Physics / Volume 115 / Issue 12 / ARTICLES / Surfaces, Interfaces, and Materials

J. Chem. Phys. 115, 5620 (2001); http://dx.doi.org/10.1063/1.1396815 (5 pages)

Direct comparisons of rates for low temperature diffusion of hydrogen and deuterium on Cu(001) from quantum mechanical calculations and scanning tunneling microscopy experiments

Jeremy Kua1, Lincoln J. Lauhon2, Wilson Ho3, and William A. Goddard1

1Materials and Process Simulation Center (139-74), California Institute of Technology, Pasadena, California 91125
2Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138
3Department of Physics and Astronomy and Department of Chemistry, University of California, Irvine, California 92697

(Received 22 January 2001; accepted 3 July 2001)

Recent experiments by Lauhon and Ho using scanning tunneling microscopy (STM) observed the direct hopping of H and D on Cu(001) as a function of temperature. They found nearly temperature independent tunneling for H below 60 K, but could not detect the tunneling threshold for D (it is at least 1000 times lower than for H). The availability of such direct and accurate measurements provides the opportunity for validating the level of theory required to predict the diffusion of adsorbates on surfaces. Thus, we carried out density functional theory (DFT) using the generalized gradient approximation (GGA-II) on periodic slabs. The calculated tunneling rate of 4.74×10−4 s−1 for H is in close agreement with the experimental value of 4.4×10−4 s−1. We predict 4.66×10−9 s−1 for the tunneling rate of D (one hop every 83 months!). Between 60 and 80 K, the calculated thermally activated diffusion rate of H is 1012.88 exp(−0.181 eV/kT) s−1 in close agreement with the STM value: 1012.9±0.3 exp(−0.197 eV/kT). For deuterium, between 50 and 80 K, the calculated rate is 1012.70 exp(−0.175 eV/kT) s−1 in close agreement with the STM value: 1012.7±0.2 exp(−0.194 eV/kT) s−1. These results validate that such first principles theory can be used to predict the diffusion (including tunneling) for adsorbates on surfaces, providing important data needed to unravel surface processes in catalysis and crystal growth. © 2001 American Institute of Physics.

© 2001 American Institute of Physics

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KEYWORDS and PACS

Keywords

copper, hydrogen neutral atoms, deuterium, scanning tunnelling microscopy, surface diffusion, adsorbed layers

PACS

  • 68.43.Jk

    Diffusion of adsorbates, kinetics of coarsening and aggregation

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.1396815

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
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