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Nonempirical (double-hybrid) density functionals applied to atomic excitation energies: A systematic basis set investigation |
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| Authors: | Laura Hernández-Martínez Eric Brémond Angel J Pérez-Jiménez Emilio San-Fabián Carlo Adamo Juan C Sancho-García |
| Institution: | 1. Department of Physical Chemistry, University of Alicante, Alicante, Spain
Contribution: Investigation;2. ITODYS, UMR CNRS 7086, Université de Paris, Paris, France Contribution: Conceptualization, Methodology, Writing - original draft;3. Department of Physical Chemistry, University of Alicante, Alicante, Spain Contribution: Formal analysis, Methodology, Writing - original draft;4. Department of Physical Chemistry, University of Alicante, Alicante, Spain Contribution: Funding acquisition, Resources, Validation, Writing - original draft;5. Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences, Paris, France;6. Department of Physical Chemistry, University of Alicante, Alicante, Spain |
| Abstract: | We investigate here the lowest-energy (spin-conserving) excitation energies for the set of He-Ne atoms, with the family of nonempirical PBE, PBE0, PBE0-1/3, PBE0-DH, PBE-CIDH, PBE-QIDH, and PBE0-2 functionals, after employing a wide variety of basis sets systematically approaching the basis set limit: def2-nVP(D), cc-pVnZ, aug-cc-pVnZ, and d-aug-cc-pVnZ. We find that an accuracy (ie, mean unsigned error) of 0.3 to 0.4 eV for time-dependent density functional theory (DFT) atomic excitation energies can be robustly achieved with modern double-hybrid methods, which are also stable with respect to the addition of a double set of diffuse functions, contrarily to hybrid versions, in agreement with recent findings employing sophisticated multiconfigurational DFT methods. |
| Keywords: | atomic excitation energies diffuse basis functions double-hybrid density functionals |