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Article Dans Une Revue Journal of Physical Chemistry A Année : 2013

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

Résumé

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-ωPBE) or to a local meta-GGA functional (LC-M06L) and two global hybrid functionals (CAM-B3LYP and ωB97x). The spectra calculated with those density functionals are in good agreement with the recent accurate experimental measurements. We show that CAM-B3LYP and ωB97x 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 selectrons.
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Dates et versions

hal-03030676 , version 1 (30-11-2020)

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Franck Rabilloud. Assessment of the Performance of Long-Range-Corrected Density Functionals for Calculating the Absorption Spectra of Silver Clusters. Journal of Physical Chemistry A, 2013, 117 (20), pp.4267-4278. ⟨10.1021/jp3124154⟩. ⟨hal-03030676⟩
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