Crystalline electric field excitations and their nonlinear splitting under magnetic fields in YbOCl

Recently reported van der Waals layered honeycomb rare-earth chalcohalides REChX (RE = rare earth, Ch = chalcogen, and <a:math xmlns:a="http://www.w3.org/1998/Math/MathML"><a:mrow><a:mi>X</a:mi></a:mrow></a:math> = halogen) are considered to be promising Kitaev spin liquid (KSL) candidates. The high-quality single crystals of YbOCl, a representative member of the family with an effective spin of 1/2, are available now. The crystalline electric field (CEF) excitations in a rare-earth spin system are fundamentally important for understanding both finite-temperature and ground-state magnetism but remain unexplored in YbOCl so far. In this paper, we conduct a comprehensive Raman scattering study to unambiguously identify the CEF excitations in YbOCl and determine the CEF parameters and wave functions. Our Raman experiments further reveal the anomalous nonlinear CEF splitting under magnetic fields. We have grown single crystals of YbOCl, the nonmagnetic LuOCl, and the diluted magnetic <b:math xmlns:b="http://www.w3.org/1998/Math/MathML"><b:msub><b:mi mathvariant="normal">Lu</b:mi><b:mrow><b:mn>0.86</b:mn></b:mrow></b:msub><b:msub><b:mi mathvariant="normal">Yb</b:mi><b:mrow><b:mn>0.14</b:mn></b:mrow></b:msub><b:mtext>OCl</b:mtext></b:math> to make a completely comparative investigation. Polarized Raman spectra on the samples at 1.8 K allow us to clearly assign all the Raman-active phonon modes and explicitly identify the CEF excitations in YbOCl. The CEF excitations are further examined using temperature-dependent Raman measurements and careful symmetry analysis based on Raman tensors related to CEF excitations. By applying the CEF Hamiltonian to the experimentally determined CEF excitations, we extract the CEF parameters and eventually determine the CEF wave functions. The study experimentally pins down the CEF excitations in the Kitaev compound YbOCl and sets a foundation for understanding its finite-temperature magnetism and exploring the possible nontrivial spin ground state. Published by the American Physical Society 2024