Chemically Accurate Excitation Energies With Small Basis Sets

Emmanuel Giner (1) , Anthony Scemama (2) , Julien Toulouse (1) , Pierre-Francois Loos (2)

1 LCT - Laboratoire de chimie théorique
2 GMO - Groupe THEO (LCPQ)

By combining extrapolated selected configuration interaction (sCI) energies obtained with the CIPSI (Configuration Interaction using a Perturbative Selection made Iteratively) algorithm with the recently proposed short-range density-functional correction for basis-set incompleteness [Giner et al.,J. Chem. Phys. 2018, 149, 194301], we show that one can get chemically accurate vertical and adiabatic excitation energies with, typically, augmented double-$\zeta$ basis sets. We illustrate the present approach on various types of excited states (valence, Rydberg, and double excitations) in several small organic molecules (methylene, water, ammonia, carbon dimer and ethylene). The present study clearly evidences that special care has to be taken with very diffuse excited states where the present correction does not catch the radial incompleteness of the one-electron basis set.

Domaines: Chimie; Chimie théorique et/ou physique

Emmanuel Giner, Anthony Scemama, Julien Toulouse, Pierre-Francois Loos. Chemically Accurate Excitation Energies With Small Basis Sets. Journal of Chemical Physics, 2019, 151 (14), pp.144118. ⟨10.1063/1.5122976⟩. ⟨hal-02289341v2⟩