JCP Nameplate
  • Volume/Page
  • Keyword
  • DOI
  • Citation
  • Advanced
   
 
 
 

You Tube Flickr Twitter UniPHY Group iResearch App Facebook

Journal of Chemical Physics / Volume 133 / Issue 16 / ARTICLES / Surfaces, Interfaces, and Materials

J. Chem. Phys. 133, 164703 (2010); http://dx.doi.org/10.1063/1.3497037 (15 pages)

Modeling the noble metal/TiO2 (110) interface with hybrid DFT functionals: A periodic electrostatic embedded cluster model study

Salai Cheettu Ammal and Andreas Heyden

Department of Chemical Engineering, University of South Carolina, 301 S. Main St., Columbia, South Carolina 29208, USA

View MapView Map

(Received 12 April 2010; accepted 14 September 2010; published online 26 October 2010)

The interaction of Aun and Ptn (n = 2,3) clusters with the stoichiometric and partially reduced rutile TiO2 (110) surfaces has been investigated using periodic slab and periodic electrostatic embedded cluster models. Compared to Au clusters, Pt clusters interact strongly with both stoichiometric and reduced TiO2 (110) surfaces and are able to enhance the reducibility of the TiO2 (110) surface, i.e., reduce the oxygen vacancy formation energy. The focus of this study is the effect of Hartree–Fock exchange on the description of the strength of chemical bonds at the interface of Au/Pt clusters and the TiO2 (110) surface. Hartree–Fock exchange helps describing the changes in the electronic structures due to metal cluster adsorption as well as their effect on the reducibility of the TiO2 surface. Finally, the performance of periodic embedded cluster models has been assessed by calculating the Pt adsorption and oxygen vacancy formation energies. Cluster models, together with hybrid PBE0 functional, are able to efficiently compute reasonable electronic structures of the reduced TiO2 surface and predict charge localization at surface oxygen vacancies, in agreement with the experimental data, that significantly affect computed adsorption and reaction energies.

© 2010 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. COMPUTATIONAL DETAILS
    1. Periodic DFT calculations
    2. Periodic electrostatic embedded cluster calculations
  3. VALIDATION OF THE PEEC MODELS
    1. Adsorption of Pt on the stoichiometric TiO2 (110) surface
    2. The partially reduced TiO2 (110) surface
    3. Cluster model for the metal-oxide interface
  4. ADSORPTION OF Aun AND Ptn (n = 2,3) CLUSTERS ON THE STOICHIOMETRIC AND REDUCED TiO2 (110) SURFACE
    1. Adsorption energies and geometries of (Mn) clusters on the TiO2 (110) surface
    2. Charge transfer between adsorbed (Mn) clusters and the TiO2 (110) surface
    3. Binding mechanism and orbital overlap between (Mn) clusters and the TiO2 (110) surface
  5. REDUCIBILITY OF THE TiO2 SURFACE
  6. CONCLUSIONS

RELATED DATABASES

To view database links for this article, you need to log in.

KEYWORDS and PACS

Keywords

adsorption, bonds (chemical), density functional theory, gold, HF calculations, interface states, metal clusters, metal-insulator boundaries, platinum, titanium compounds

PACS

  • 73.40.-c

    Electronic transport in interface structures

  • 68.43.Mn

    Adsorption kinetics

  • 71.15.Ap

    Basis sets (LCAO, plane-wave, APW, etc.) and related methodology (scattering methods, ASA, linearized methods, etc.)

  • 71.15.Mb

    Density functional theory, local density approximation, gradient and other corrections

  • 73.20.At

    Surface states, band structure, electron density of states

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3497037

PUBLICATION DATA

ISSN

0021-9606 (print)  
1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef American Institute of Physics

For access to fully linked references, you need to log in.
    O. Dulub, W. Hebenstreit, and U. Diebold, Phys. Rev. Lett. 84, 3646 (2000).

    L. Zhang, R. Persaud, and T. E. Madey, Phys. Rev. B 56, 10549 (1997).

    G. Pacchioni, J. Chem. Phys. 128, 182505 (2008)JCPSA6000128000018182505000001
    J. L. F. Da Silva, M. V. Ganduglia-Pirovano, J. Sauer, V. Bayer, and G. Kresse, Phys. Rev. B 75, 045121 (2007).

    C. Di Valentin, G. Pacchioni, and A. Selloni, Phys. Rev. Lett. 97, 166803 (2006).

    A. M. Burow, M. Sierka, J. Dobler, and J. Sauer, J. Chem. Phys. 130, 174710 (2009)JCPSA6000130000017174710000001.

    J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).

    G. Makov and M. C. Payne, Phys. Rev. B 51, 4014 (1995).

    J. Harris, Phys. Rev. B 31, 1770 (1985), W. Matthew C. Foulkes and R. Haydock, ibid. 39, 12520 (1989).

    J. P. Perdew, M. Emzerhof, and K. Burke, J. Chem. Phys. 105, 9982 (1996)JCPSA6000105000022009982000001.

    P. J. Hay and W. R. Wadt, J. Chem. Phys. 82, 270 (1985)JCPSA6000082000001000270000001.

    A. Schäfer, C. Huber, and R. Ahlrichs, J. Chem. Phys. 100, 5829 (1994)JCPSA6000100000008005829000001.

    J. A. Pople, M. Headgordon, D. J. Fox, K. Raghavachari, and L. A. Curtiss, J. Chem. Phys. 90, 5622 (1989)JCPSA6000090000010005622000001.

    H. Iddir, S. Ogut, N. D. Browning, and M. M. Disko, Phys. Rev. B 72, 081407 (2005), 73, 039902(E) (2006).

    H. Iddir, V. Skavysh, S. Ogut, N. D. Browning, and M. M. Disko, Phys. Rev. B 73, 041403 (2006).

    A. E. Reed, R. B. Weinstock, and F. Weinhold, J. Chem. Phys. 83, 735 (1985)JCPSA6000083000002000735000001.

    P. Reinhardt, M. Causa, C. M. Marian, and B. A. Hess, Phys. Rev. B 54, 14812 (1996).

    A. D. Becke, J. Chem. Phys. 98, 5648 (1993)JCPSA6000098000007005648000001.

    S. Chrétien and H. Metiu, J. Chem. Phys. 127, 244708 (2007)JCPSA6000127000024244708000001.

    X. Y. Wu, A. Selloni, and S. K. Nayak, J. Chem. Phys. 120, 4512 (2004)JCPSA6000120000009004512000001.

    A. Vijay, G. Mills, and H. Metiu, J. Chem. Phys. 118, 6536 (2003)JCPSA6000118000014006536000001
    M. D. Rasmussen, L. M. Molina, and B. Hammer, ibid. 120, 988 (2004)JCPSA6000120000002000988000001
    K. J. Hameeuw, G. Cantele, D. Ninno, F. Trani, and G. Iadonisi, ibid. 124, 024708 (2006)JCPSA6000124000002024708000001
    S. J. Thompson and S. P. Lewis, Phys. Rev. B 73, 073403 (2006), T. Bredow, L. Giordano, F. Cinquini, and G. Pacchioni, ibid. 70, 035419 (2004).

    G. K. H. Madsen and B. Hammer, J. Chem. Phys. 130, 044704 (2009)JCPSA6000130000004044704000001.

    S. Chrétien and H. Metiu, J. Chem. Phys. 127, 084704 (2007)JCPSA6000127000008084704000001.

    T. Pabisiak and A. Kiejna, Phys. Rev. B 79, 085411 (2009).

    T. Tamura, S. Ishibashi, K. Terakura, and H. M. Weng, Phys. Rev. B 80, 195302 (2009).


For access to citing articles, you need to log in.


Figures (7) Tables (8)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)

Access to article objects (figures, tables, multimedia) requires a subscription; log in to view available files.
(Access to supplementary files, where available, is free for this journal.)


Close

Google Calendar

ADVERTISEMENT

Your Recent History Recent History Help

Recently Viewed

  1. Modeling the noble metal/TiO2 (110) interface with hybrid DFT functionals: A periodic electrostatic embedded cluster model study
  2. Liquid to quasicrystal transition in bilayer water
  3. The applicability of three-dimensional aromaticity in BiSnn− Zintl analogues
  4. Publisher’s note: “Molecular correlations and solvation in simple fluids” [ J. Chem. Phys. 132, 214506 (2010) ]
  5. Fluctuation power spectra reveal dynamical heterogeneity of peptides
Go to AIP Home
Copyright © American Institute of Physics
close