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Positively charged metal–ammonia complexes are known to host peripheral, diffuse electrons around their molecular skeleton. The resulting neutral species form materials known as expanded or liquid metals. Alkali, alkaline earth, and transition metals have been investigated previously in experimental and theoretical studies of both the gas and condensed phase. This work is the first ab initio exploration of an f-block metal–ammonia complex. The ground and excited states are calculated for Th0–3+ complexes with ammonia, crown ethers, and aza-crown ethers. For Th3+ complexes, the one valence electron Th populates the metal’s 6d or 7f orbitals. For Th0–2+, the additional electrons prefer occupation of the outer s- and p-type orbitals of the complex, except Th(NH3)10, which uniquely places all four electrons in outer orbitals of the complex. Although thorium coordinates up to ten ammonia ligands, octa-coordinated complexes are more stable. Crown ether complexes have a similar electronic spectrum to ammonia complexes, but excitations of electrons in the outer orbitals of the complex are higher in energy. Aza-crown ethers disfavor the orbitals perpendicular to the crowns, attributed to the N-H bonds pointing along the plane of the crowns.