Experimental evaluation of the stabilization of the COT orbitals by 4f orbitals in COT2Ce using a Hubbard model

Lukens, Wayne W.; Booth, Corwin H.; Walter, Marc D.

doi:10.1039/d0dt03897k

Experimental evaluation of the stabilization of the COT orbitals by 4f orbitals in COT₂Ce using a Hubbard model

Journal Article · Thu Jan 21 23:00:00 EST 2021 · Dalton Transactions

DOI:https://doi.org/10.1039/d0dt03897k· OSTI ID:1827986

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Technische Universität Braunschweig (Germany)

Significant orbital mixing is rare in lanthanide complexes because of the limited radial extent of the 4f orbitals, which results in a generally small stabilization due to 4f orbital interactions. Nevertheless, even a small amount of additional stabilization could enhance lanthanide separations. One lanthanide complex in which orbital mixing has been extensively studied both experimentally and computationally is cerocene, COT₂Ce, where COT is cyclooctatetraene. This compound has a singlet ground state with a low-lying, triplet excited state. Previous fluorescence studies on trimethylsilyl-substituted cerocenes indicate the triplet state is 0.4 eV higher in energy than the singlet state. In addition, computational studies predict that the triplet is 0.3 to 1 eV higher in energy than the singlet. The synthesis of highly pure COT₂Ce by Walter and Andersen allowed its physical properties to be accurately measured. Using these measurements, we evaluate the stabilization of the 4f orbitals using two, independent approaches. A Hubbard model is used to evaluate the stabilization of the ground state due to orbital mixing. This stabilization, which is also the singlet–triplet gap, is –0.29 eV using this model. Furthermore, this gap was also from the temperature independent paramagnetism of COT₂Ce, which yielded a value of –0.32 eV.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1827986

Alternate ID(s):: OSTI ID: 1763825

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 7 Vol. 50; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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