Yb$^{3+}$ $f$-$f$ excitations in NaYbSe$_2$: benchmarking embedded-cluster quantum chemical schemes for 4$f$ insulators

TL;DR

This study uses ab initio quantum chemical methods to accurately predict the $f$-$f$ excitation spectrum of NaYbSe$_2$, benchmarking computational schemes against experimental neutron scattering data for Yb$^{3+}$ ions.

Contribution

It demonstrates the effectiveness of configuration-interaction calculations with single and double substitutions in reproducing experimental excitation energies in 4$f$ insulators.

Findings

Computed excitation energies agree within 3-4 meV with experimental data.

Embedded-cluster quantum chemical schemes are validated as efficient tools.

The approach offers an alternative to model-Hamiltonian fitting for $f$-center multiplet analysis.

Abstract

$\tilde{S}\!=\!1/2$ triangular-lattice $f$-electron materials define a dynamic research area in condensed matter magnetism. In various Yb 4$f^{13}$ triangular-lattice compounds, for example, spin-liquid ground states seem to be realized. Using {\it ab initio} quantum chemical methods, we here investigate how correlation effects involving the 4$f$ electrons affect the on-site $f$-$f$ excitation spectrum in NaYbSe$_2$. The system is well suited for such a study since unambiguous inelastic neutron scattering data are available for the Yb$^{3+}$ $f$-$f$ transitions. The excitation energies obtained by configuration-interaction calculations with single and double substitutions agree within 3-4 meV with experimental values, which provides a not so expensive alternative to fitting experimental data at the model-Hamiltonian level in order to analyze $f$-center multiplet structures.