We present an experimental and theoretical study of the absorption and emission spectra of Yb atoms in a solid Ne matrix at a resolution of 0.025 nm. Five absorption bands were identified as due to transitions from the $4f^{14}5d^06s^2 ^1!S_0$ ground state configuration to $4f^{14}5d^06s6p$ and $4f^{13}5d^16s^2$ configurations. The two lowest energy bands were assigned to outer-shell transitions to $6s6p ^3P_1$ and $^1P_1$ atomic states and displayed the structure of a broad doublet and an asymmetric triplet, respectively. The remaining three higher-frequency bands were assigned to inner-shell transitions to distinct $J=1$ states arising from the $4f^{13}5d^16s^2$ configuration and were highly structured with narrow linewidths. A classical simulation was performed to identify the stability and symmetry of possible trapping sites in the Ne crystal. It showed that the overarching 1+2 structure of the high frequency bands could be predominantly ascribed to crystal field splitting in the axial field of a 10-atom vacancy of $C_{4v}$ symmetry. Their prominent substructures were shown to be manifestations of phonon sidebands associated with the zero-phonon lines on each crystal field state. Unprecedented for a metal-rare gas system, resolution of individual phonon states on an allowed electronic transition was possible under excitation spectroscopy which reflects the semi-quantum nature of solid Ne. In contrast to the absorption spectra, emission spectra produced by steady-state excitation into the $^1P_1$ absorption band consisted of simple, unstructured fluorescence bands.
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