The complex Rydberg structure of ytterbium atoms is shaped by multiple low-lying ion-core-excited states and strong channel interactions, which presents both opportunities and challenges for quantum information processing and precision metrology. In this work, we extend high-resolution microwave spectroscopy and multichannel quantum defect theory (MQDT) modeling of singly excited Rydberg states in Yb and Yb to include the () and () series. Our measurements reveal - mixing in odd-parity Rydberg states of Yb, which we incorporate by combined MQDT models for and series. Additionally, we observe that for the spin-orbit interaction dominates over the exchange interaction, such that the states are more accurately described in a -coupled basis. We validate our models by comparing the predicted Landé -factors and static dipole polarizabilities with experimental measurements, finding excellent agreement. These results provide important input for designing high-fidelity entangling gates with ytterbium atoms.

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