Achieving ultranarrow absorption linewidths in the condensed phase enables optical state preparation of specific non-thermal states, a prerequisite for quantum-enabled technologies. The 4f orbitals of lanthanide(III) complexes are often referred to as “atom-like,” reflecting their isolated nature, and are promising substrates for the optical preparation of specific quantum states. To better understand the photophysical properties of 4f states and assess their potential for quantum applications, theoretical building blocks are required for rapid screening. In this study, an atomic-level perturbative calculation (i.e., spin–orbit crystal field, SOCF) is applied to various Yb(III) complexes to investigate their linear absorption and emission through a fitting mechanism of their experimentally determined transition energies and oscillator strengths. In particular, the optical properties of (thiolfan)YbCl(THF) (thiolfan = 1,1′-bis(2,4-di-tert-butyl-6-thiomethylenephenoxy)ferrocene), a recently reported complex with an ultranarrow optical linewidth, are computed and compared to those of other Yb(III) compounds. Through a transition energy sampling study, major contributors to the optical linewidth are identified. We observe particularly isolated f–f transitions and narrow linewidths, which we attribute to two distinct factors. Firstly, the ultra-high atomic similarity of the orbitals involved in the optical transition, along with the presence of an anisotropic crystal field, collectively contribute to the observed narrow transitions. Secondly, we note highly correlated excited-ground energy fluctuations that serve to greatly suppress inhomogeneous line-broadening. This article illustrates how SOCF can be used as a low-cost method to probe the influence of crystal field environment on the optical properties of Yb(III) complexes to assist the development of novel lanthanide series quantum materials.
