Jump rates for surface diffusion of large molecules from first principles

We apply a recently developed stochastic model for the surface diffusion of large molecules to calculate jump rates for 9,10-dithioanthracene on a Cu(111) surface. The necessary input parameters for the stochastic model are calculated from first principles using density functional theory (DFT). We f...

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Bibliographic Details
Published in:The Journal of chemical physics 2015-04, Vol.142 (15), p.154105-154105
Main Authors: Shea, Patrick, Kreuzer, Hans Jürgen
Format: Article
Language:English
Subjects:
ADSORPTION
CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS
COPPER
CORRECTIONS
CRYSTAL STRUCTURE
DAMPING
DENSITY FUNCTIONAL METHOD
Density functional theory
DIFFUSION BARRIERS
Diffusion rate
ENERGY TRANSFER
First principles
Mathematical models
MOLECULES
PHONONS
Stochastic models
STOCHASTIC PROCESSES
Surface diffusion
SURFACES
VAN DER WAALS FORCES
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Summary:We apply a recently developed stochastic model for the surface diffusion of large molecules to calculate jump rates for 9,10-dithioanthracene on a Cu(111) surface. The necessary input parameters for the stochastic model are calculated from first principles using density functional theory (DFT). We find that the inclusion of van der Waals corrections to the DFT energies is critical to obtain good agreement with experimental results for the adsorption geometry and energy barrier for diffusion. The predictions for jump rates in our model are in excellent agreement with measured values and show a marked improvement over transition state theory (TST). We find that the jump rate prefactor is reduced by an order of magnitude from the TST estimate due to frictional damping resulting from energy exchange with surface phonons, as well as a rotational mode of the diffusing molecule.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4917484