This study employed relativistic methods to investigate the connection between the conformation and bonding properties of 45 lanthanide trihalides LnX 3 (Ln: La−Lu; X:F, Cl, Br). Our findings reveal several insights. The proper symmetry exhibited by open-shell LnX 3 requires the inclusion of spin−orbit coupling, achieved with 2-component relativistic Hamiltonians. Fluorines (LnF 3) primarily exhibit pyramidal structures, while chlorides and bromides tend to yield planar conformations. For a given halide, the strength of Ln−X bonds increases across the lanthanide series, another outcome of the lanthanide contraction. Both strength and covalency of Ln−X bonds decrease upon the halide, i.e., LnF 3 > LnCl 3 > LnBr 3. We introduced a novel parameter, the local force constant associated with the dihedral β(X−Ln−X−X), k a (β), which quantifies the resistance of these molecules to conformational changes. We observed a correlation between k a (β) and the covalency of the Ln−X bond, with higher k a (β) values indicating a stronger covalent character. Finally, the degree of pyramidalization in the LnX 3 structures is connected to (i) the extent of charge donation within the molecule and (ii) the greater covalency of the Ln−X bond. These findings provide valuable insights into the interplay between the electronic structure and molecular geometry in LnX 3. ■ INTRODUCTION Lanthanide trihalides LnX 3 , where Ln represents one of the 15 lanthanide elements, 1,2 ranging from lanthanum (La, atomic number 57) to lutetium (Lu, atomic number 71) in the formal oxidation state +3, and X represents a halogen (fluorine, chlorine, bromine, or iodine), have attracted much attention over the past decades due to their unique chemical, electronic, and optical properties. The broad application spectrum of Lanthanide trihalides and their complexes include their use as luminescent materials 3,4 e.g. in phosphors for lighting and display technologies, or scintillators for radiation detection; 5 optic materials; 6 magnetic materials, e.g., in magnetic refrigeration technology; 7 or precursors for the synthesis of lanthanide-containing semiconductors, 2 to name a few. Lanthanides trifluorides have raised interest in the nuclear industry 6 as these compounds can be formed in certain nuclear reactors. In computational chemistry, LnX 3 often serve as models for larger Ln coordination compounds of higher complexity, and as test targets benchmarking for relativistic methodologies and basis sets 8−10 featuring 4f elements. Despite their popularity which has initiated numerous experiments and theoretical studies, 6,11−14 there are still open questions regarding their structure, bonding, and molecular properties, as discussed in a recent communication. 15 There is still an ongoing debate on which factors determine if an LnX 3 compound is planar (D 3h symmetry) or pyramidal (C 3v symmetry). The small conversion barriers between the two conformations, e.g., 0.41 kcal/mol for LaF 3 , make both experimental and computational investigations of this question rather difficult. 13,14 Most authors associate LnF 3 with pyramidal and heavier halides with a planar structure for the majority of Ln(III). 14,16,17 However, the question of what causes a lanthanide trihalide to be planar or pyramidal has not been fully answered yet, as it results from a complex interplay between steric hindrance and electronic effects typical of heavy metals. 18 Possible explanations for favoring pyramidalization are polarization and d/f orbital participation in bonding, whereas planar arrangements seem to be favored by larger halides with lower polarizability, exhibiting pronounced ionic Ln−X bonds. 14,17 Molnar and Hargittai 12 proposed a model based on a number of competing factors, namely the asphericity of the 4f shell, the Ln polarizability, and the halide electronegativity. According to their empirical model, the f electron shape predominantly influences the conformation of