Journal article
Computational Investigation of the Effect of Transition Metal Coordination in Bimetallic Uranylpyridine-Dicarboxylate Complexes
ACS Physical Chemistry Au
07/31/2026
DOI: 10.1021/acsphyschemau.6c00096
Abstract
Understanding how secondary metal coordination perturbs uranyl electronic structure is important for developing structure-property relationships in actinide-containing materials relevant to separations, waste management, and environmental chemistry. In this work, periodic and cluster density functional theory calculations were used to investigate the structural, electronic, and vibrational properties of monometallic U-2,6-pyridinedicarboxylic acid (PDC) and heterometallic U-PDC-TM complexes (TM = Fe, Co, Ni, Cu, and Zn). Incorporating transition metal (TM) changes the valence-band electronic structure of the U-PDC-TM framework due to TM d and ligand O 2p contributions near the band edge and reduces the bandgap across most of the series. The nature of these states is supported by the frontier molecular orbital diagrams constructed from the cluster models. Charge redistribution is observed along the TM octahedral unit and the bridging ligand framework rather than direct interaction with the uranyl center. Simulated Raman vibrational modes agree reasonably well with experiments for the ligand ring bending and breathing modes, although subtle TM-dependent changes in the uranyl stretching mode were not consistently captured across the full series. The phonon modes show a blue shift in the uranyl symmetric stretch consistent with experiments when Ni is incorporated into the U-PDC structure, indicating U≡O bond strengthening. The change in the partial charges on the U center confirms a small electron density accumulation due to the presence of TMs. Our results show that incorporating secondary TM provides a viable strategy for tuning the electronic properties of uranyl coordination complexes through indirect ligand-mediated coupling.
Details
- Title: Subtitle
- Computational Investigation of the Effect of Transition Metal Coordination in Bimetallic Uranylpyridine-Dicarboxylate Complexes
- Creators
- Keerthan R. Rao - Idaho National LaboratoryHeather J. Culbertson - University of Notre DameShuxiang Zhou - Idaho National LaboratoryPeter C. Burns - University of Notre DameTori Z. Forbes - University of IowaAshini S. Jayasinghe - Idaho National Laboratory
- Resource Type
- Journal article
- Publication Details
- ACS Physical Chemistry Au
- DOI
- 10.1021/acsphyschemau.6c00096
- ISSN
- 2694-2445
- eISSN
- 2694-2445
- Publisher
- American Chemical Society
- Grant note
- INL Laboratory Directed Research&Development (LDRD) Program: DE-AC07-05ID14517 Office of Science Graduate Research fellowship program: NA
This work was supported through the INL Laboratory Directed Research & Development (LDRD) Program under DOE Idaho Operations Office Contract DE-AC07-05ID14517. H.C. was supported by the Office of Science Graduate Research fellowship program. This research made use of the Idaho National Laboratory's High Performance Computing systems located at the Collaborative Computing Center and supported by the Office of Nuclear Energy of the U.S. Department of Energy and the Nuclear Science User Facilities under Contract No. DE-AC07-05ID14517. This research also made use of computational resources provided by the Notre Dame Center for Research Computing.
- Language
- English
- Electronic publication date
- 07/31/2026
- Academic Unit
- Civil and Environmental Engineering; Core Research Facilities; Chemistry
- Record Identifier
- 9985217830402771
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