Ab Initio Calculations on the Ground and Excited Electronic States of Thorium–Ammonia, Thorium–Aza-Crown, and Thorium–Crown Ether Complexes

Lu, Zhongyuan; Jackson, Benjamin A.; Miliordos, Evangelos

doi:10.3390/molecules28124712

Ab Initio Calculations on the Ground and Excited Electronic States of Thorium–Ammonia, Thorium–Aza-Crown, and Thorium–Crown Ether Complexes

Journal Article · Mon Jun 12 00:00:00 EDT 2023 · Molecules

DOI:https://doi.org/10.3390/molecules28124712· OSTI ID:1984897

Lu, Zhongyuan; Jackson, Benjamin A.;

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.

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Research Organization:: Auburn Univ., AL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0019177

OSTI ID:: 1984897

Alternate ID(s):: OSTI ID: 2421009

Journal Information:: Molecules, Journal Name: Molecules Journal Issue: 12 Vol. 28; ISSN MOLEFW; ISSN 1420-3049

Publisher:: MDPI AGCopyright Statement

Country of Publication:: Switzerland

Language:: English

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Ab Initio Calculations on the Ground and Excited Electronic States of Thorium–Ammonia, Thorium–Aza-Crown, and Thorium–Crown Ether Complexes

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