Modeling the electronic structures of the ground and excited states of the ytterbium atom and the ytterbium dimer: A modern quantum chemistry perspective

Abstract

We present a comprehensive theoretical study of the electronic structures of the Yb atom and the Yb${}_2$ molecule, respectively, focusing on their ground and lowest-lying electronically excited states. Our study includes various state-of-the-art quantum chemistry methods such as CCSD, CCSD(T), CASPT2 (including spin--orbit coupling), and EOM-CCSD as well as some recently developed pCCD-based approaches and their extensions to target excited states. Specifically, we scan the lowest-lying potential energy surfaces of the \ce{Yb2} dimer and provide a reliable benchmark set of spectroscopic parameters including optimal bond lengths, vibrational frequencies, potential energy depths, and adiabatic excitation energies. Our in-depth analysis unravels the complex nature of the electronic spectrum of \ce{Yb2}, which is difficult to model accurately by any conventional quantum chemistry method. Finally, we scrutinize the bi-excited character of the first ${}^1{\Sigma }_g^{+}$ excited state and its evolution along the potential energy surface.

arXiv comment31 pages, 2 figures, Version of Record

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• Delving into the Catalytic Mechanism of Molybdenum Cofactors: A Novel Coupled Cluster Study
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• Reexamination of the ground state Born-Oppenheimer Yb${}_2$ potential
• Tuning Domain-Based Charge Transfer in Organic Dyes: Impact of Heteroatom Doping on the $\pi$-Linker of Carbazole-Based Systems
• Ionization Potentials at Mean-Field Computational Cost: The Extended Koopmans' Framework for pCCD