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Author Rabilloud, Franck
Source United States Department of Energy Office of Scientific and Technical Information
Content type Text
Language English
Subject Keyword INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ♦ NANOSCIENCE AND NANOTECHNOLOGY ♦ ABSORPTION SPECTRA ♦ COLLECTIVE EXCITATIONS ♦ DENSITY FUNCTIONAL METHOD ♦ ELECTRONS ♦ HARTREE-FOCK METHOD ♦ HYBRIDIZATION ♦ NANOSTRUCTURES ♦ SILVER ♦ SIMULATION ♦ TIME DEPENDENCE
Abstract Absorption spectra of Ag{sub 20} and Ag{sub 55}{sup q} (q = +1, −3) nanoclusters are investigated in the framework of the time-dependent density functional theory in order to analyse the role of the d electrons in plasmon-like band of silver clusters. The description of the plasmon-like band from calculations using density functionals containing an amount of Hartree-Fock exchange at long range, namely, hybrid and range-separated hybrid (RSH) density functionals, is in good agreement with the classical interpretation of the plasmon-like structure as a collective excitation of valence s-electrons. In contrast, using local or semi-local exchange functionals (generalized gradient approximations (GGAs) or meta-GGAs) leads to a strong overestimation of the role of d electrons in the plasmon-like band. The semi-local asymptotically corrected model potentials also describe the plasmon as mainly associated to d electrons, though calculated spectra are in fairly good agreement with those calculated using the RSH scheme. Our analysis shows that a portion of non-local exchange modifies the description of the plasmon-like band.
ISSN 00219606
Educational Use Research
Learning Resource Type Article
Publisher Date 2014-10-14
Publisher Place United States
Journal Journal of Chemical Physics
Volume Number 141
Issue Number 14


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