Electronic spectra of ytterbium fluoride from relativistic electronic structure calculations

Johann V. Pototschnig*, Kenneth G. Dyall, Lucas Visscher, André Severo Pereira Gomes

*Corresponding author for this work

Research output: Contribution to JournalArticleAcademicpeer-review


We report an investigation of the low-lying excited states of the YbF molecule-a candidate molecule for experimental measurements of the electron electric dipole moment-with 2-component based multi-reference configuration interaction (MRCI), equation of motion coupled cluster (EOM-CCSD) and the extrapolated intermediate Hamiltonian Fock-space coupled cluster (XIHFS-CCSD). Specifically, we address the question of the nature of these low-lying states in terms of configurations containing filled or partially-filled Yb 4f shells. We show that while it does not appear possible to carry out calculations with both kinds of configurations contained in the same active space, reliable information can be extracted from different sectors of Fock space-that is, by performing electron attachment and detachment IHFS-CCSD and EOM-CCSD calculation on the closed-shell YbF+ and YbF- species, respectively. From these calculations we predict Ω = 1/2, 3/2 states, arising from the 4f13σ26s, 4f145d1/6p1, and 4f135d1σ16s configurations to be able to interact as they appear in the same energy range around the ground-state equilibrium geometry. As these states are generated from different sectors of Fock space, they are almost orthogonal and provide complementary descriptions of parts of the excited state manifold. To obtain a comprehensive picture, we introduce a simple adiabatization model to extract energies of interacting Ω = 1/2, 3/2 states that can be compared to experimental observations.

Original languageEnglish
Pages (from-to)22330-22343
Number of pages14
JournalPhysical Chemistry Chemical Physics
Issue number39
Early online date1 Oct 2021
Publication statusPublished - 21 Oct 2021

Bibliographical note

Funding Information:
L. V. and J. V. P. wish to thank The Netherlands Organization for Scientific Research (NWO) for financial support via the ECHO and computer time. J. V. P. acknowledges funding by the Austrian Science Fund (FWF):J 4177-N36. ASPG acknowledges support from PIA ANR project CaPPA (ANR-11-LABX-0005-01), the Franco-German project CompRIXS (Agence nationale de la recherche ANR-19-CE29-0019, Deutsche Forschungsgemeinschaft JA 2329/6-1), I-SITE ULNE projects OVERSEE, the French Ministry of Higher Education and Research, region Hauts de France council and European Regional Development Fund (ERDF) project CPER CLIMIBIO, and the French national supercomputing facilities (grants DARI A0070801859 and A0090801859). A. S. P. G., L. H., J. P. and L. V. acknowledge support from MESONM International Associated Laboratory (LAI) (ANR-16-IDEX-0004).

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