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

Journal Article · Mon Dec 07 00:00:00 EST 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3265767· OSTI ID:21559811

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

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1. 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)
2. Center for Computational Physics, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal)
3. 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)
4. 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)

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.

• OSTI ID: 21559811
• Journal Information: Journal of Chemical Physics, Vol. 131, Issue 21; Other Information: DOI: 10.1063/1.3265767; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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