Nonempirical (double‐hybrid) density functionals applied to atomic excitation energies: A systematic basis set investigation
| Autor: | Juan Carlos Sancho-García, Emilio San-Fabián, Éric Brémond, Carlo Adamo, Ángel J. Pérez-Jiménez, Laura Hernández-Martínez |
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| Přispěvatelé: | Universidad de Alicante. Departamento de Química Física, Química Cuántica |
| Rok vydání: | 2020 |
| Předmět: |
Engineering
010304 chemical physics business.industry Science and engineering Atomic excitation energies Library science Advanced materials Double-hybrid density functionals 010402 general chemistry Condensed Matter Physics 01 natural sciences Atomic and Molecular Physics and Optics 0104 chemical sciences Work (electrical) Internship 0103 physical sciences Diffuse basis functions Química Física Physical and Theoretical Chemistry business Basis set |
| Zdroj: | RUA. Repositorio Institucional de la Universidad de Alicante Universidad de Alicante (UA) |
| Popis: | 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. L.H.M. acknowledges the “Instituto Universitario de Materiales (IUMA)” for a research internship. The work in Alicante is supported by the projects AICO/2018/175 from the Regional Government (GVA/FSE) and FIS2015-64222-C2-2-P from the “Ministerio de Ciencia, Innovación y Universidades”. E.B. thanks ANR (“Agence Nationale de la Recherche”) and CGI (“Commissariat à l'Investissement d'Avenir”) for financial support through Labex SEAM (Science and Engineering for Advanced Materials and devices) ANR 11 LABX 086, ANR 11 IDEX 05 02. |
| Databáze: | OpenAIRE |
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