Optical Absorption Spectra of Ag11 Isomers by First-Principles Theoretical Spectroscopy with Time-dependent Density Functional Theory

Abstract

The optical absorption spectrum of the three most stable isomers of the Ag11 system was calculated using the time-dependent density functional theory, with the generalized gradient approximation for the exchange and correlation potential, and a relativistic pseudopotential parametrization for the modelling of the ion-electron interaction. The computational scheme is based on a real space code, where the photoabsorption spectrum is calculated by using the formalism developed by Casida. The significantly different spectra of the three isomers permit the identification of the ground-state configuration predominantly present in the laboratory beams in base to a comparison between the calculated photoabsorption spectrum of the most stable configuration of Ag11 and the measured spectra of medium-size silver clusters trapped in noble gas Ar and Ne matrices at different temperatures. This assignment is confirmed by the fact that this isomer has the lowest calculated energy.