Computational Modeling of Reactive f-element Separations

Volatile f-metal complexes have been used in a variety of applications including separations and thin film deposition. To identify ligand design contributions that promote differential volatility of f-metal complexes, the undergraduate student in the Vlaisavljevich group will conduct DFT and wavefunction-based calculations to identify correlations between differences in metal-ligand covalency, intermolecular forces, and molecular structures with the compounds’ volatilities. The calculations will be used to evaluate how different ligand substituents affect metal-ligand bonding and charge distribution in lanthanide and actinide complexes. The goal is to minimize attractive intermolecular forces and maximize electron-electron repulsions in the solid state that help to drive molecules apart in the gas phase. By quantifying these differences, we can deeply understand experimental observations and predict the volatilities of target complexes prior to their synthesis. Previous dispersion corrected-DFT calculations by our group on similar systems successfully determined the reaction thermodynamics for monomeric, dimeric, and oligomeric f-element borohydride complexes.

Selected Publications

1. T. V. Fetrow, R. Bhowmick, A. J. Achazi, A. V. Blake, F. D. Eckstrom, B. Vlaisavljevich, and S. R. Daly “Chelating Borohydrides for Lanthanides and Actinides: Structures, Mechanochemistry, and Case Studies with Phosphinodiboranates” Inorg. Chem. 2020, 59, 48-61.; DOI:10.1021/acs.inorgchem.9b01628

2. A. Blake, T. Fetrow, Z. Theiler, B. Vlaisavljevich, and S. Daly. “Homoleptic Uranium and Lanthanide Phosphinodiboronates” Chem. Commun. 2018, 54, 5602–5606.; DOI:10.1039/C8CC02862A

3. B. Vlaisavljevich, P. Miró, D. Koballa, T. Todorova, C. J. Cramer, L. Gagliardi, S. Daly, and G. Girolami. “Volatilities of Actinide and Lanthanide N,N–Dimethylaminodiboranate CVD Precursors: A DFT Study” J. Phys. Chem. C 2012, 116 (44), 23194–23200; DOI:10.1021/jp305691y