Assessment of the Performance of Long-Range-Corrected Density Functionals for Calculating the Absorption Spectra of Silver Clusters

作者：Rabilloud Franck^*

来源：Journal of Physical Chemistry A, 2013, 117(20): 4267-4278.

DOI：10.1021/jp3124154

We assess the accuracy of several long-range-corrected (LC-) density functionals for the prediction of absorption spectra of silver clusters by time-dependent density functional theory. Several types of LC-functionals, with the exact Hartree-Fock exchange at long-range, are used: those applying the long-range correction to a standard GGA-type functional (LC-BP86, LC-omega PBE) or to a local meta-GGA functional (LC-M06L) and two global hybrid functionals (CAM-B3LYP and omega 97x). The spectra calculated with those density functionals are in good agreement with the recent accurate experimental measurements. We show that CAM-B3LYP and omega B97x are some of the most accurate functionals for evaluating the electronic excitation energies, while LC-M06L is more effective in reducing the occurrence of spurious states. The long-range correction appears to be essential in describing the absorption spectra of large clusters. The description of the plasmon-like band with LC functionals as transitions associated with excitations from s orbitals to s + p orbitals is in fairly good agreement with the classical interpretation as a collective excitation of valence s electrons.

• 出版日期2013-5-23