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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
https://doi.org/10.1021/acs.jpclett.6b02024
Copyright © 2016 American Chemical Society

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    Abstract

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    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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    6. Helen Chadwick, Yosef Alkoby, Joshua T. Cantin, Dennis Lindebaum, Oded Godsi, Tsofar Maniv, Gil Alexandrowicz. Molecular spin echoes; multiple magnetic coherences in molecule surface scattering experiments. Physical Chemistry Chemical Physics 2021, 23 (13) , 7673-7681. https://doi.org/10.1039/D0CP05399F
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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) https://doi.org/10.1063/5.0024178
    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) https://doi.org/10.1103/PhysRevA.101.062703
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    11. Riccardo Ferrando, Andrew P. Jardine. Surface Diffusion. 2020, 45-70. https://doi.org/10.1007/978-3-030-46906-1_2
    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. https://doi.org/10.1016/j.cpc.2019.04.013
    13. Renan Villarreal, Christopher J. Kirkham, Alessandro Scarfato, David R. Bowler, Christoph Renner. Towards surface diffusion potential mapping on atomic length scale. Journal of Applied Physics 2019, 125 (18) https://doi.org/10.1063/1.5091736
    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. https://doi.org/10.1016/j.susc.2018.04.019
    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. https://doi.org/10.1039/C7FD00095B

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