Probing the performances of HISS functionals for the description of excited states of molecular systems

Romain Paulino Neto (1) , Denis Jacquemin (2) , Carlo Adamo (3) , Ilaria Ciofini (4)

1 LCMCP (site ENSCP) - Laboratoire de Chimie de la Matière Condensée de Paris (site ENSCP)
2 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
3 ENSCP - Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL
4 LECIME - Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575)

The performances of two range-separated functionals (HISS-A and HISS-B), recently developed by Savin and collaborators, and including a fraction of HF exchange for an intermediate range of interelectronic distance, have been tested for the prediction of vertical excited state energies over three benchmark sets of molecules mainly probing valence and intramolecular charge-transfer transitions in small- to medium-size organic compounds. The results obtained show that HISS-B outperforms HISS-A providing results that are, for singlet-to-singlet excitations, at least in line with those of more traditional long-range-separated hybrids such as LC-PBE or CAM-B3LYP possessing the correct asymptotic behavior and, in the case of larger compounds, close to those provided by global hybrids.

Domaines: Chimie

Romain Paulino Neto, Denis Jacquemin, Carlo Adamo, Ilaria Ciofini. Probing the performances of HISS functionals for the description of excited states of molecular systems. Theoretical Chemistry Accounts: Theory, Computation, and Modeling, 2013, 132 (11), ⟨10.1007/s00214-013-1396-y⟩. ⟨hal-02142399⟩