Chemically Accurate Excitation Energies With Small Basis Sets

02 July 2019, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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-ζ 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.

Keywords

density functional theory
range-separated DFT
full CI
excitation energy
adiabatic energy
excited states

Supplementary materials

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Description
Actions
Title
Ex-srDFT-SI
Description
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