Absorption of Some Small Silver Clusters: DFT and Caspt2 Calculations

Abstract

Two quantum chemical methods which are the time-dependent density functional theory (TD-DFT) and the complete active space CASPT2/CASSCF have been used in modeling absorption spectra of silver clusters Ag n (n = 2, 3, 4, 6, 8). There is an overall good agreement between TD-DFT and CASPT2 results for transition energies. The absorption spectra of the Ag n clusters examined can reasonably be simulated using the excitation energies obtained by either TD-DFT or CASPT2 method. The main result emerged from this calculation is that the TD-DFT method is suitable for treatment of excited states of Ag clusters. The choice of specific functionals and basis sets to be used in some cases induces important effects on the calculated spectra. It is also noteworthy to mention that for some clusters, the neutral Ag 6 for instance, the effect of noble gas environment is significant, while for some others such as the neutral Ag 8 , it is not. Therefore, carrying out TD-DFT calculations to reproduce and to assign a given structure to an experimental absorption spectrum of a silver cluster, it is not only to select suitable functionals but also to take enough effects of environments into account.