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Journal of Chemical Physics / Volume 136 / Issue 6 / ARTICLES / Condensed Phase Dynamics, Structure, and Thermodynamics: Spectroscopy, Reactions, and Relaxation

J. Chem. Phys. 136, 064502 (2012); http://dx.doi.org/10.1063/1.3676409 (17 pages)

Structure and properties of metal-exchanged zeolites studied using gradient-corrected and hybrid functionals. II. Electronic structure and photoluminescence spectra

Florian Göltl and Jürgen Hafner

Fakultät für Physik and Center for Computational Materials Science, Universität Wien, Sensengasse 8/12, A-1090 Wien, Austria

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(Received 12 October 2011; accepted 21 December 2011; published online 8 February 2012)

The influence of the choice of the exchange-correlation functional (semilocal gradient corrected or hybrid functionals) on the electronic properties of metal-exchanged zeolites has been investigated for Cu- and Co-exchanged chabazite. The admixture of exact exchange in hybrid functionals increases the fundamental gap of purely siliceous chabazite, leading to better agreement with experiment and many-body perturbation theory for close-packed SiO2 polymorphs where detailed experimental information is available. For the metal-exchanged chabazite the increased exchange splitting strongly influences the position of the cation states relative to the framework bands—in general, gradient-corrected functionals locate the occupied cation states close to the valence-band maximum of the framework, while hybrid functionals shift the occupied cation states to larger binding energies and the empty states to higher energies within the fundamental gap. The photoluminescence spectra have been analyzed using fixed-moment total-energy calculations for excited spin states in structurally relaxed and frozen geometries. The geometrical relaxation of the excited states leads to large differences in excitation and emission energies which are more pronounced in calculations using hybrid functionals. Due to the stronger relaxation effects calculated with hybrid functionals, the large differences in the electronic spectra calculated with both types of functionals are not fully reflected in the photoluminescence spectra.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. FUNCTIONALS AND COMPUTATIONAL SETUP
  3. ELECTRONIC SPECTRUM OF PURELY SILICEOUS CHABAZITE
  4. ELECTRONIC SPECTRUM OF TM-EXCHANGED ZEOLITES
    1. Cu(I)-chabazite
      1. Ground state: Spin singlet
      2. Excited state: Spin triplet
    2. Cu(II)-chabazite
      1. Ground state: Spin doublet
      2. Excited state: Spin quadruplet
    3. Co(II)-chabazite
      1. Ground state: Spin quadruplet
      2. Excited low- and high-spin states
  5. PHOTOLUMINESCENCE SPECTROSCOPY OF ELECTRONIC EXCITATIONS
    1. DRS spectrum of Cu(I)-chabazite
    2. DRS spectra of Cu(II)-chabazite
    3. DRS spectra of Co(II)-chabazite
  6. DISCUSSION
  7. CONCLUSIONS

EDITORIALLY RELATED

    Related Articles

  1. Structure and properties of metal-exchanged zeolites studied using gradient-corrected and hybrid functionals. I. Structure and energetics
    Florian Göltl et al.
    J. Chem. Phys. 136, 064501 (2012)JCPSA6000136000006064501000001
  2. Structure and properties of metal-exchanged zeolites studied using gradient-corrected and hybrid functionals. III. Energetics and vibrational spectroscopy of adsorbates
    Florian Göltl et al.
    J. Chem. Phys. 136, 064503 (2012)JCPSA6000136000006064503000001

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KEYWORDS and PACS

Keywords

electron correlations, exchange interactions (electron), excited states, many-body problems, molecular configurations, perturbation theory, photoluminescence, positive ions, total energy, valence bands, zeolites

PACS

  • 33.15.Bh

    General molecular conformation and symmetry; stereochemistry

  • 33.50.-j

    Fluorescence and phosphorescence; radiationless transitions, quenching (intersystem crossing, internal conversion)

  • 31.15.vq

    Electron correlation calculations for polyatomic molecules

  • 31.15.xp

    Perturbation theory

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3676409

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.
    A. V. Krukau, O. A. Vydrov, A. F. Izmaylov, and G. Scuseria, J. Chem. Phys. 125, 224106 (2006)JCPSA6000125000022224106000001.

    Y. Wang and J. P. Perdew, Phys. Rev. B 43, 8911 (1991).

    Y. Xu and W. Y. Ching, Phys. Rev. B 44, 11048 (1991).

    Z. A. Weinberg, G. W. Rubloff, and E. Bassous, Phys. Rev. B 19, 3107 (1979).

    L. E. Ramos, J. Furthmüller, and F. Bechstedt, Phys. Rev. B 69, 085102 (2004).


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