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Mass Transport in Surface Diffusion of van der Waals Bonded Systems: Boosted by Rotations?

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School of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA, U.K.
Cavendish Laboratory, University of Cambridge, JJ Thomson Avenue, Cambridge CB3 0HE, U.K.
Department of Chemistry, University of Surrey, Guildford GU2 7XH, U.K.
§ The Perse School, Cambridge CB2 8QF, U.K.
Department of Chemistry, Technion - Israel Institute of Technology, Haifa 32000, Israel
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, U.K.
Cite this: J. Phys. Chem. Lett. 2016, 7, 23, 4819–4824
Publication Date (Web):November 10, 2016
Copyright © 2016 American Chemical Society

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    Abstract Image

    Mass transport at a surface is a key factor in heterogeneous catalysis. The rate is determined by excitation across a translational barrier and depends on the energy landscape and the coupling to the thermal bath of the surface. Here we use helium spin–echo spectroscopy to track the microscopic motion of benzene adsorbed on Cu(001) at low coverage (θ ∼ 0.07 ML). Specifically, our combined experimental and computational data determine both the absolute rate and mechanism of the molecular motion. The observed rate is significantly higher by a factor of 3.0 ± 0.1 than is possible in a conventional, point-particle model and can be understood only by including additional molecular (rotational) coordinates. We argue that the effect can be described as an entropic contribution that enhances the population of molecules in the transition state. The process is generally relevant to molecular systems and illustrates the importance of the pre-exponential factor alongside the activation barrier in studies of surface kinetics.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpclett.6b02024.

    • Further details of the Bayesian method, Langevin MD simulations, and DFT calculations, including a table of the calculated adsorption energies (PDF)

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    Cited By

    This article is cited by 15 publications.

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    8. Mila Miletic, Karol Palczynski, Joachim Dzubiella. Quantifying entropic barriers in single-molecule surface diffusion. The Journal of Chemical Physics 2020, 153 (16)
    9. J. T. Cantin, G. Alexandrowicz, R. V. Krems. Transfer-matrix theory of surface spin-echo experiments with molecules. Physical Review A 2020, 101 (6)
    10. Ryan T. Hannagan, Kyle Groden, Amanda M. Larson, Andrew J. Therrien, Theodore Thuening, Alex C. Schilling, Jean-Sabin McEwen, E. Charles H. Sykes. Visualizing the origin of rotational entropy effects in coadsorbed systems. Physical Review Research 2020, 2 (2)
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    12. N. Avidor, P.S.M. Townsend, D.J. Ward, A.P. Jardine, J. Ellis, W. Allison. PIGLE — Particles Interacting in Generalized Langevin Equation simulator. Computer Physics Communications 2019, 242 , 145-152.
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    14. Andrew R. Alderwick, Andrew P. Jardine, William Allison, John Ellis. An evaluation of the kinematic approximation in helium atom scattering using wavepacket calculations. Surface Science 2018, 678 , 65-71.
    15. M. Sacchi, P. Singh, D. M. Chisnall, D. J. Ward, A. P. Jardine, W. Allison, J. Ellis, H. Hedgeland. The dynamics of benzene on Cu(111): a combined helium spin echo and dispersion-corrected DFT study into the diffusion of physisorbed aromatics on metal surfaces. Faraday Discussions 2017, 204 , 471-485.

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