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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, 064503 (2012); http://dx.doi.org/10.1063/1.3676410 (31 pages)

Structure and properties of metal-exchanged zeolites studied using gradient-corrected and hybrid functionals. III. Energetics and vibrational spectroscopy of adsorbates

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 exchange-correlation functional (semilocal gradient corrected or hybrid functional) on density-functional studies of the adsorption of CO and NO in Cu- and Co-exchanged chabazite has been investigated, extending the studies of the structural and electronic properties of these materials [F. Göltl and J. Hafner, J. Chem. Phys. 136, 064501 (2012)10.1063/1.3676408; F. Göltl and J. Hafner, J. Chem. Phys. 136, 064502 (2012)10.1063/1.3676409] and including for comparison carbonyls and nitrosyls of Cu and Co. Hybrid functionals predict much lower adsorption energies than conventional semilocal functionals, in better agreement with experiment as far as data are available for comparison. The calculated adsorption energies show a strong linear correlation with the stability of the cation sites. For Cu(I)-chabazite the calculated adsorption energies span almost the interval between the adsorption energies calculated for pure neutral and positively charged Cu-carbonyls and nitrosyls. For divalent Cu(II) and Co(II) the adsorption energies at cations in chabazite are much lower than the metal-molecule binding energies in the free carbonyls or nitrosyls, especially for the most stable cation location in a six-membered ring of the chabazite structure. For the stretching modes of adsorbed CO only hybrid functionals reproduce the blueshift of the frequency reported for all Cu(I)- and Co(II)-zeolites. For Cu(II)-chabazite both types of functionals predict a blueshift, the larger value calculated with hybrid functionals being in better agreement with observation. For NO adsorbed on Cu(I)-chabazite all functionals produce a redshift, the smaller value derived with hybrid functionals being in better agreement with experiment. For NO adsorbed in Cu(II)- and Co(II)-chabazite gradient-corrected functionals produce the best agreement with experiment for cations located in a six-membered ring. Semilocal functionals tend to underestimate the frequencies, while hybrid functionals tend to overestimate. The decisive factors determining the influence of the functionals are the larger HOMO-LUMO gap and the larger bandgap of the zeolite host, as well as the larger exchange-splitting of the cation eigenstates predicted with hybrid functionals. For Co(II)-chabazite the tendency to overestimate the exchange-splitting and to stabilize a high-spin state lead to better results with semilocal functionals. Finally, a comprehensive discussion of the influence of the exchange-correlation functional on the physico-chemical properties of these complex systems, based all three papers of this series is presented.

© 2012 American Institute of Physics

Article Outline

  1. INTRODUCTION
  2. FUNCTIONALS AND COMPUTATIONAL SETUP
  3. GAS-PHASE CARBONYLS AND NITROSYLS
    1. TM-carbonyls
    2. TM-nitrosyls
  4. ADSORPTION OF CO IN CU- AND CO-EXCHANGED CHABAZITE
    1. CO adsorbed on Cu(I)-chabazite
      1. Structure and energetics
      2. Stretching frequencies
      3. Bonding and electronic structure
    2. CO adsorbed on Cu(II)-chabazite
      1. Structure and energetics
      2. Stretching frequencies
      3. Bonding and electronic structure
    3. CO adsorbed on Co(II)-chabazite
      1. Structure and energetics
      2. Stretching frequencies
      3. Bonding and electronic structure
    4. Summary CO adsorption
  5. ADSORPTION OF NO
    1. NO adsorbed on Cu(I)-chabazite
      1. Structure and energetics
      2. Stretching frequencies
      3. Electronic structure and bonding
    2. NO adsorbed on Cu(II)-chabazite
      1. Structure and energetics
      2. Stretching frequencies
      3. Electronic structure and bonding
    3. NO adsorbed on Co(II)-chabazite
      1. Structure and energetics
      2. Stretching frequencies
      3. Electronic structure and bonding
    4. Summary NO adsorption
  6. DISCUSSION AND CONCLUSION

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. II. Electronic structure and photoluminescence spectra
    Florian Göltl et al.
    J. Chem. Phys. 136, 064502 (2012)JCPSA6000136000006064502000001

RELATED DATABASES

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KEYWORDS and PACS

Keywords

adsorbed layers, adsorption, binding energy, carbon compounds, density functional theory, energy gap, molecular configurations, nitrogen compounds, positive ions, red shift, vibrational states, zeolites

PACS

  • 68.43.Mn

    Adsorption kinetics

  • 31.15.eg

    Exchange-correlation functionals (in current density functional theory)

  • 33.15.Bh

    General molecular conformation and symmetry; stereochemistry

  • 33.15.Ry

    Ionization potentials, electron affinities, molecular core binding energy

  • 33.20.Tp

    Vibrational analysis

  • 33.70.Jg

    Line and band widths, shapes, and shifts

ARTICLE DATA

Digital Object Identifier
http://dx.doi.org/10.1063/1.3676410

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).

    A. Stroppa, K. Termentzidis, J. Paier, G. Kresse, and J. Hafner, Phys. Rev. B 76, 195440 (2007).

    I. Georgieva, L. Benco, D. Tunega, N. Trendafilova, H. Lischka, and J. Hafner, J. Chem. Phys. 131, 054101 (2009)JCPSA6000131000005054101000001.

    M. Zhou and L. Andrews, J. Chem. Phys. 111, 4548 (1999)JCPSA6000111000010004548000001.

    Y. Zhang and W. Yang, Phys. Rev. Lett. 80, 890 (1997).


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