Photoabsorption spectra of small cationic xenon clusters from time-dependent density functional theory

Oliveira, Micael J. T.; Nogueira, Fernando; Marques, Miguel A. L.; Rubio, Angel

doi:10.1063/1.3265767

Title: Photoabsorption spectra of small cationic xenon clusters from time-dependent density functional theory

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Abstract

Upon ionization, rare-gas (like Ar and Xe) clusters shift their absorption spectrum from the ultraviolet to the visible. This happens as bonding becomes much stronger due to the removal of an electron from a strongly antibonding orbital. In this article, we study the absorption spectrum of small cationic xenon clusters (Xe{sub n}{sup +}, with n=3,...,35) by means of time-dependent density functional theory. These calculations include relativistic effects through the use of relativistic j-dependent pseudopotentials in a two-spinor formulation of the Kohn-Sham equations. The peak positions in our calculated spectra are in fairly good agreement with experiment and confirm that absorption is mainly due to a charged linear core composed of 3, 4, or 5 Xe atoms where the positive charge is localized. However, we find large deviations concerning the oscillator strengths, which can be partially explained by the unsatisfactory treatment of exchange in common density functionals. Furthermore, we find that adequate ground-state geometries are necessary for the correct prediction of the qualitative features of the spectra.

Authors:

Oliveira, Micael J. T. ^[1]; Nogueira, Fernando ^[2]; Marques, Miguel A. L. ^[3]; Rubio, Angel ^[4]

Center for Computational Physics, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal) and Laboratoire de Physique de la Matiere Condense et Nanostructures, Universite Lyon I, CNRS, UMR 5586, Domaine Scientifique de la Doua, F-69622 Villeurbanne Cedex (France)
Center for Computational Physics, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal)
Laboratoire de Physique de la Matiere Condense et Nanostructures, Universite Lyon I, CNRS, UMR 5586, Domaine Scientifique de la Doua, F-69622 Villeurbanne Cedex (France)
Dpto. Fisica de Materiales, Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Universidad del Pais Vasco, Centro de Fisica de Materiales CSIC-UPV/EHU-MPC and DIPC, Av. Tolosa 72, E-20018 San Sebastian (Spain)

Publication Date:: Mon Dec 07 00:00:00 EST 2009

OSTI Identifier:: 21559811

Resource Type:: Journal Article

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 131; Journal Issue: 21; Other Information: DOI: 10.1063/1.3265767; (c) 2009 American Institute of Physics; Journal ID: ISSN 0021-9606

Country of Publication:: United States

Language:: English

Subject:: 74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ATOMIC CLUSTERS; ATOMS; CATIONS; DENSITY FUNCTIONAL METHOD; ELECTRONS; EQUATIONS; FORECASTING; GROUND STATES; OSCILLATOR STRENGTHS; PEAKS; PHOTOIONIZATION; PHOTON-ATOM COLLISIONS; POTENTIALS; RELATIVISTIC RANGE; TIME DEPENDENCE; ULTRAVIOLET RADIATION; XENON; ATOM COLLISIONS; CALCULATION METHODS; CHARGED PARTICLES; COLLISIONS; ELECTROMAGNETIC RADIATION; ELEMENTARY PARTICLES; ELEMENTS; ENERGY LEVELS; ENERGY RANGE; FERMIONS; FLUIDS; GASES; IONIZATION; IONS; LEPTONS; NONMETALS; PHOTON COLLISIONS; RADIATIONS; RARE GASES; SPECTRA; VARIATIONAL METHODS

Citation Formats


                    Oliveira, Micael J. T., European Theoretical Spectroscopy Facility, Nogueira, Fernando, Marques, Miguel A. L., European Theoretical Spectroscopy Facility, Rubio, Angel, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6 D-14 195 Berlin-Dahlem, and European Theoretical Spectroscopy Facility. Photoabsorption spectra of small cationic xenon clusters from time-dependent density functional theory.  United States: N. p., 2009. 
        Web.  doi:10.1063/1.3265767.

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                    Oliveira, Micael J. T., European Theoretical Spectroscopy Facility, Nogueira, Fernando, Marques, Miguel A. L., European Theoretical Spectroscopy Facility, Rubio, Angel, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6 D-14 195 Berlin-Dahlem, & European Theoretical Spectroscopy Facility. Photoabsorption spectra of small cationic xenon clusters from time-dependent density functional theory.  United States.  https://doi.org/10.1063/1.3265767

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                    Oliveira, Micael J. T., European Theoretical Spectroscopy Facility, Nogueira, Fernando, Marques, Miguel A. L., European Theoretical Spectroscopy Facility, Rubio, Angel, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6 D-14 195 Berlin-Dahlem, and European Theoretical Spectroscopy Facility. 2009.  
        "Photoabsorption spectra of small cationic xenon clusters from time-dependent density functional theory".  United States.  https://doi.org/10.1063/1.3265767.

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@article{osti_21559811,

  title        = {Photoabsorption spectra of small cationic xenon clusters from time-dependent density functional theory},

  author       = {Oliveira, Micael J. T. and European Theoretical Spectroscopy Facility and Nogueira, Fernando and Marques, Miguel A. L. and European Theoretical Spectroscopy Facility and Rubio, Angel and Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6 D-14 195 Berlin-Dahlem and European Theoretical Spectroscopy Facility},

  abstractNote = {Upon ionization, rare-gas (like Ar and Xe) clusters shift their absorption spectrum from the ultraviolet to the visible. This happens as bonding becomes much stronger due to the removal of an electron from a strongly antibonding orbital. In this article, we study the absorption spectrum of small cationic xenon clusters (Xe{sub n}{sup +}, with n=3,...,35) by means of time-dependent density functional theory. These calculations include relativistic effects through the use of relativistic j-dependent pseudopotentials in a two-spinor formulation of the Kohn-Sham equations. The peak positions in our calculated spectra are in fairly good agreement with experiment and confirm that absorption is mainly due to a charged linear core composed of 3, 4, or 5 Xe atoms where the positive charge is localized. However, we find large deviations concerning the oscillator strengths, which can be partially explained by the unsatisfactory treatment of exchange in common density functionals. Furthermore, we find that adequate ground-state geometries are necessary for the correct prediction of the qualitative features of the spectra.},

  doi          = {10.1063/1.3265767},

  url          = {https://www.osti.gov/biblio/21559811},
  journal      = {Journal of Chemical Physics},

  issn         = {0021-9606},

  number       = 21,

  volume       = 131,

  place        = {United States},

  year         = {Mon Dec 07 00:00:00 EST 2009},

  month        = {Mon Dec 07 00:00:00 EST 2009}

}

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