Surfaces and Interfaces

Surfaces and interfaces have been decidedly considered to harbor interesting phenomena that have yet to be understood which opened doors to new applications in the field of catalysis, electronic devices, and sensors, to name a few. Our group has been actively exploring the chemical and elctronic properties of surfaces and interfaces of diverse metal oxides through Density Functional Theory, Molecular Dynamics simulations, and Monte Carlo methods. For example, with DFT+thermodynamics in tandem with experimental methods that can probe the spatial ordering and electronc structure of surfaces, such as Low Energy Electron Diffraction (LEED) and Scanning Tunneling Microscopy M), we could identify the atomic strucrure of surfaces, with atomic level information.

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Recent related works

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In a joint effort with the Bonnell Group from Penn's Laboratory of Research on the Structure of Matter (LRSM), we explore the (001) surface reconstruction of BaTiO3 with periodicity of (√5× √5) R26.6°.

J. M. P. Martirez, E. H. Morales, W. A. Saidi, D. A. Bonnell, and A. M. Rappe, "Atomic and Electronic Structure of the BaTiO3(001) (√5× √5) R26.6° Surface Reconstruction", Phys. Rev. Lett. 109, 256802 (1-5) (2012). PDF

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We study the agglomeration behavior of Pd deposited on polar LiNbO3 (0001) surface. We find that positively-polar surface prefers clustering of Pd atoms while a much more disperssed configuration is favored on negatively-polar surface.

S. Kim, M. Rutenberg Schoenberg, and A. M. Rappe, "Polarization Dependence of Palladium Deposition on Ferroelectric Lithium Niobate (0001) Surfaces", Phys. Rev. Lett. 107, 076102 (1-5) (2011). PDF Supplementary material PDF

Related publications

  • J. M. P. Martirez, E. H. Morales, W. A. Saidi, D. A. Bonnell, and A. M. Rappe, "Atomic and Electronic Structure of the BaTiO3(001) (√5× √5) R26.6° Surface Reconstruction", Phys. Rev. Lett. 109, 256802 (1-5) (2012). PDF
  • S. Kim, M. Rutenberg-Schoenberg, and A. M. Rappe, "Kinetics of palladium particles on LiNbO3: an origin of the polarization¬≠dependent¬†catalysis", MRS Proceedings 1397, 12-01 (1-7) (2012). PDF
  • M. A. Méndez Polanco, I. Grinberg, A. M. Kolpak, S. V. Levchenko, C. Pynn, and A. M. Rappe, "Stabilization of highly polarized PbTiO3 nanoscale capacitors due to in-plane symmetry breaking at the interface", Phys. Rev. B 85, 214107 (1-7) (2012). PDF
  • Z. Luo, S. Kim, N. Kawamoto, A. M. Rappe, and A. T. C. Johnson, "Growth Mechanism of Hexagonal-Shape Graphene Flakes with Zigzag Edges", ACS Nano 5, 9154-60 (2011). PDF
  • S. Kim, M. Rutenberg Schoenberg, and A. M. Rappe, "Polarization Dependence of Palladium Deposition on Ferroelectric Lithium Niobate (0001) Surfaces", Phys. Rev. Lett. 107, 076102 (1-5) (2011). PDF Supplementary material PDF
  • S. E. Mason, E. A. Sokol, V. R. Cooper, and A. M. Rappe, "Spontaneous Formation of Dipolar Metal Nanoclusters", J. Phys. Chem. A 113, 4134-7 (2009). PDF
  • R. V. Wang, D. D. Fong, F. Jiang, M. J. Highland, P. H. Fuoss, C. Thompson, A. M. Kolpak, J. A. Eastman, S. K. Streiffer, A. M. Rappe, and G. B. Stephenson, "Reversible chemical switching of a ferroelectric film", Phys. Rev. Lett. 102, 047601 (1-4) (2009). PDF
  • A. M. Kolpak, D. Li, R. Shao, A. M. Rappe, and D. A. Bonnell, "Evolution of the structure and thermodynamic stability of the BaTiO3 (001) surface", Phys. Rev. Lett. 101, 036102 (1-4) (2008). PDF Supplementary material PDF
  • S. V. Levchenko and A. M. Rappe, "Influence of ferroelectric polarization on the equilibrium stoichiometry of lithium niobate (0001) surfaces", Phys. Rev. Lett.100, 256101 (1-4) (2008). PDF
  • D. Li, M. H. Zhao, J. Garra, A. M. Kolpak, A. M. Rappe, D. A. Bonnell, and J. M. Vohs, "Direct in situ determination of the polarization dependence of physisorption on ferroelectric surfaces," Nat. Mat. 7 473-7 (2008). PDF
  • S. E. Mason, I. Grinberg, and A. M. Rappe, "Orbital-specific Analysis of CO Chemisorption on Transition-Metal Surfaces", J. Phys. Chem. C 112, 1963-6 (2008). PDF
  • A. M. Kolpak, I. Grinberg, and A. M. Rappe, "Polarization effects on the surface chemistry of PbTiO3-supported Pt films", Phys. Rev. Lett. 98 166101 (1-4) (2007). PDF
  • J. Li, U. G. Singh, J. W. Bennett, K. Page, J. Weaver, J.-P. Zhang, T. Proffen, A. M. Rappe, S. Scott, and R. Seshadri, "BaCe1-xPdxO3-δ (0≤x≤ 0.1): Redox controlled ingress and egress of palladium in a perovskite", Chem. Mater. 19, 1418-26 (2007). PDF
  • V. R. Cooper, A. M. Kolpak, Y. Yourdshahyan, and A. M. Rappe, "Oxide-supported metal thin-film catalysts: the how and why?", Nanotechnology in catalysis, Vol. 3, B. Zhou, ed., Springer-Verlag New York, pp. 13-21 (2006). PDF
  • S. E. Mason, I. Grinberg and A. M. Rappe, "Adsorbate-adsorbate interactions and chemisorption at different coverages studied by accurate ab initio calculations: CO on transition metal surfaces", J. Phys. Chem. B 110, 3816-22 (2006). PDF
  • V. R. Cooper, A. M. Kolpak, Y. Yourdshahyan, and A. M. Rappe, "Supported metal electronic structure: implications for molecular adsorption", Phys. Rev. B Rapid Comm. 72, 081409(R) (1-4) (2005). Selected for the Virtual Journal of Nanoscale Science and Technology, September 12, 2005 issue. PDF
  • M.-L. Bocquet, A. M. Rappe, and H.-L. Dai, "A density functional theory study of adsorbate-induced work function change and binding energy: Olefins on Ag(111)", Molecular Physics 103, 883-90 (2005). PDF
  • Y. Yourdshahyan, V. R. Cooper, A. M. Kolpak, and A. M. Rappe, "Catalytic behavior at the nanoscale: CO adsorption on Al2O3-supported Pt clusters", Proc. SPIE 5223, 223-31 (2004). PDF
  • S. E. Mason, I. Grinberg, and A. M. Rappe, " First-principles extrapolation method for accurate CO adsorption energies on metal surfaces", Phys. Rev. B Rapid Comm. 69, 161401R (1-4) (2004). PDF
  • E. J. Walter and A. M. Rappe, "Coadsorption of methyl radicals and oxygen on Rh (111)", Surf. Sci. 549, 265-72 (2004). PDF
  • R. P. Kauffman and A. M. Rappe, ``Vacancies below the (111) surface of Pd'', Phys. Rev. B 67, 085403 (1-6) (2003). PDF
  • Y. Yourdshahyan and A. M. Rappe, ``Structure and energetics of alkanethiol adsorption on the Au(111) surface'', J. Chem. Phys. 117, 825-33 (2002). PDF
  • I. Grinberg, Y. Yourdshahyan, and A. M. Rappe, ``CO on Pt(111) puzzle: A possible solution'', J. Chem. Phys. 117, 2264-2270 (2002). PDF
  • X. Lin, N. J. Ramer, A. M. Rappe, K. Hass, W. F. Schneider, and B. L. Trout, ``Effect of Particle Size on the Adsorption of O and S Atoms on Pt: a Density Functional Study'', J. Phys. Chem. B 105, 7739-7747 (2001). PDF
  • E. J. Walter, S. P. Lewis, and A. M. Rappe, ``First-principles study of carbon monoxide adsorption on zirconia-supported copper'', Surf. Sci. 495, 44-50 (2001). PDF
  • Y. Yourdshahyan, H. K. Zhang, and A. M. Rappe, ``$n$-Alkyl thiol group interactions with the Au (111) surface'', Phys. Rev. B Rapid Comm. 081405 (1-4) (2001). PDF
  • E. J. Walter, S. P. Lewis, and A. M. Rappe, ``Investigation of chemisorbed molecular states for oxygen on rhodium (111)'', J. Chem. Phys. 113, 4388-4391 (2000). PDF
  • E. J. Walter and A. M. Rappe, ``Accurate and efficient determination of chemisorption energies using pseudopotentials,'' Surf. Sci. 427-428, 11-14 (1999). PDF
  • S. P. Lewis and A. M. Rappe, ``Structural and vibrational properties of carbon monoxide adlayers on the copper (001) surface'', J. Chem. Phys. 110, 4619-4633 (1999). PDF
  • E. J. Walter, S. P. Lewis, and A. M. Rappe, "Internally consistent predictions of surface structural relaxations", Laser Techniques for Surface Science III, Proc. SPIE 3272, 196-200 (1998). PDF
  • S. P. Lewis, M. V. Pykhtin, E. J. Mele, and A. M. Rappe, "Continuum elastic theory of adsorbate vibrational relaxation", J. Chem. Phys. 108, 1157-61 (1998). PDF
  • S. P. Lewis and A. M. Rappe, "Bonding and vibrational properties of CO-adsorbed copper", Symposium Mater. Res. Soc. 391-9 (1996). PDF PDF
  • S. P. Lewis and A. M. Rappe, "Substrate-adsorbate coupling in CO-adsorbed copper", Phys. Rev. Lett. 77, 5241-4 (1996). PDF
  • S. P. Lewis and A. M. Rappe, "Quantum-mechanical investigation of bonding and vibrational properties of CO-adsorbed copper", Proc. SPIE 2547, 227-39 (1995). PDF
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