Towards an accurate description of reactions on surfaces

Prof. dr. Geert-Jan Kroes

The ability to accurately predict the outcome of elementary reactions of molecules with metal surfaces is a prerequisite to the ability to make accurate predictions of many heterogeneously catalyzed processes, which are used in the production of the majority of chemicals. My research is focused on achieving chemical accuracy in the description of reactive scattering of molecules from metal surfaces. To this purpose my group is working towards improved accuracy in the description of the interaction of molecules with metal surfaces, and incorporating surface phonon motion and electron-hole pair excitation in dynamical models of molecule-surface reactions.

Quantum dynamics of dissociative chemisorption of hydrogen and other diatomic molecules on metal surfaces

It is possible to treat the dynamics of the dissociation of hydrogen on metal surfaces quantum mechanically, while taking into account the motion in all six molecular degrees of freedom without making approximations. Because the approximations of neglecting surface phonons and electron-hole pair excitation are reasonable for many experiments on reactive scattering of H2 from metal surfaces, this makes these systems ideal for testing the accuracy of electronic structure methods for molecule-surface reactions. 



We have recently introduced a new implementation of specific reaction parameter DFT (SRP-DFT), and shown that this allows a chemically accurate description of many reactive scattering experiments on the benchmark H2 + Cu(111) reaction. Also, it turns out that the SRP density functional for H2 + Cu(111) is transferable to H2 interacting with another low index face of copper, i.e., the (100) face. 



In new research, we are investigating whether SRP-DFT can also be made to work for H2 interacting with other metal surfaces, and for other diatomic molecules (e.g., N2) reacting with metal surfaces. We are also investigating the effect of phonons and intend to investigate the effect of electron-hole pair excitation on reactions of molecules at metal surfaces. 



For an overview of the exciting questions that need to be addressed for these reactions, see the papers "Frontiers in Surface Scattering Simulations, G.J. Kroes, Science 321, 794-797 (2008)", and "Towards chemically accurate simulation of molecule-surface reactions, G.J. Kroes, Phys. Chem. Chem. Phys.14, 14966-14981 (2012)".

Quantum dynamics of dissociative chemisorption of CH4 on metal surfaces

The dissociation of CH4 into CH3 + H on a metal surface is the rate determining step in processes which produce hydrogen, such as steam reforming and catalytic partial oxidation. Ultimately, we want to study the dissociation of methane on Ni(111) and Pt(111) quantum mechanically while taking into account all degrees of freedom of the molecule. A major challenge we are working on is how to represent the 15-dimensional potential energy surface. An important goal of the research is to establish the reasons for vibrational selectivity of reaction (pre-excitation of specific vibrational modes enhances the reaction more than of other modes).  


As performing full-dimensional quantum dynamical calculations on these system is quite challenging, we are also testing the Ab Initio Molecular Dynamics (AIMD) method for these systems. One of our goals is to derive specific reaction parameter density functionals capabale of describing these reactions with chemical accuracy. An extra challenge to be addressed is that for this approach to work it will also be necessary to treat the surface phonons accurately.


For an overview of the exciting questions that need to be addressed for these reactions, see  the paper "Frontiers in Surface Scattering Simulations, G.J. Kroes, Science 321, 794-797 (2008)", and "Towards chemically accurate simulation of molecule-surface reactions, G.J. Kroes, Phys. Chem. Chem. Phys.14, 14966-14981 (2012)". For first results of the group, see our recent paper "Ab Initio Molecular Dynamics Calculations versus Quantum-State Resolved Experiments on CHD3 + Pt(111): New Insights into a Prototypical Gas-Surface Reaction, F. Nattino, H. Ueta, H. Chadwick, M. van Reijzen, R.D. Beck, B. Jackson, M.C. van Hemert, and G.J. Kroes, J.Phys.Chem.Lett.5, 1294-1299 (2014)".

Production and storage of hydrogen

In this research line, we investigate methods of producing and storing hydrogen. In particular, we aim to determine the mechanism of photo-oxidation of water on oxidic semi-conductor surfaces (as part of the photo-eletrolysis of water), and the mechanism of solid state reactions through which hydrogen can be stored in promising new compounds (for instance, alanates). For an overview of the important questions that need to be addressed for these reactions, and the results achieved by us and collaborators in the framework of research done by the Marie-Curie Research Training Network Hydrogen, see "Solar hydrogen production with semiconductor metal oxides: New directions in experiment and theory, Á.Valdés, J. Brillet, M. Grätzel, H.A. Hansen, H. Jónsson, P. Klüpfel, G.J. Kroes, F. Le Formal, I.C. Man, R.S. Martins, J.K. Nørskov, J. Rossmeisl, K. Sivula, A. Vojvodic, and M. Zäch, Phys.Chem.Chem.Phys.14, 49-70 (2012)" and "A multifaceted approach to the hydrogen storage problem, A.J. Churchard, E. Banach, A. Borgschulte, R. Caputo, J.C. Chen, D.C. Clary, K.J. Fijalkowski, J.J.C. Geerlings, R.V. Genova, W. Grochala, T. Jaron, J.C. Juanes-Marcos, B. Kasemo, G.J. Kroes, I. Ljubic, N. Naujoks, J.K. Nørskov, R.A. Olsen, F. Pendolino, A. Remhof, L. Románszki, A. Tekin, T. Vegge, M. Zäch, A. Züttel, Phys.Chem.Chem.Phys.13, 16955-16972 (2011)".

  1. Nattino, F., D. Migliorini, G.-J. Kroes, E. Dombrowski, E.A. High, D.R. Killelea, A.L. Utz, "Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction", The Journal of Physical Chemistry Letters, vol. 7, issue 13, pp. 2402 - 2406, 07/2016. DOI: 10.1021/acs.jpclett.6b01022
  2. Kroes, G.-J., "Toward a Database of Chemically Accurate Barrier Heights for Reactions of Molecules with Metal Surfaces", The Journal of Physical Chemistry Letters, vol. 6, issue 20, pp. 4106 - 4114, 10/2015. DOI: 10.1021/acs.jpclett.5b01344
  3. Blanco-Rey, M., J.  I. Juaristi, R. Díez Muiño, H.  F. Busnengo, G.  J. Kroes, M. Alducin, "Electronic Friction Dominates Hydrogen Hot-Atom Relaxation on Pd(100)", Physical Review Letters, vol. 112, issue 10, 3/2014. DOI: 10.1103/PhysRevLett.112.103203
  4. Nattino, F., H. Ueta, H. Chadwick, M.E. van Reijzen, R.D. Beck, B. Jackson, M.C. van Hemert, G.-J. Kroes, "Ab Initio Molecular Dynamics Calculations versus Quantum-State-Resolved Experiments on CHD3 + Pt(111): New Insights into a Prototypical Gas–Surface Reaction", The Journal of Physical Chemistry Letters, vol. 5, issue 8, pp. 1294 - 1299, 04/2014. DOI: 10.1021/jz500233n
  5. Nattino, F., C. Díaz, B. Jackson, G.-J. Kroes, "Effect of Surface Motion on the Rotational Quadrupole Alignment Parameter of", Physical Review Letters, vol. 108, issue 23, 6/2012. DOI: 10.1103/PhysRevLett.108.236104
  6. Diaz, C., E. Pijper, R.A. Olsen, H.F. Busnengo, D.J. Auerbach, G.J. Kroes, "Chemically Accurate Simulation of a Prototypical Surface Reaction: H-2 Dissociation on Cu(111)", Science, vol. 326, no. 5954, pp. 832-834, Nov 6, 2009. DOI: 10.1126/Science.1178722

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