The electronic properties of silver clusters Agn (n=4-20) are examined in the framework of Density Functional Theory (DFT) using several different methods of representing the exchange-correlation functional.  Three types of exchange-correlation functionals are used: those including gradient corrections to the density in the generalized gradient approximation, global hybrid functionals mixing in a portion of the Hartree-Fock exchange, and long-range corrected (LC-) functionals.  Comparison of ionization potentials calculated using DFT to experimental results demonstrate that LC-functionals more accurately represent the electronic structure of the silver clusters studied.  Absorption spectra are compared to both experimental spectra and those derived using higher level theoretical calculations showing that the LC-functionals appear to correctly describe the optical transitions in the gas phase.  It is also demonstrated that the LC-hybrid functionals significantly reduce the occurrence of spurious states in optical absorbance spectra while maintaining the intensity of the plasmon-like features of larger silver clusters.

Describing the electronic and optical properties of silver clusters using long-range corrected functionals

240th National Meeting (2010)

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