Evaluating the nature of chemical bonding for actinide elements represents one of the most important and long-standing problems in actinide science. In this work, we directly address this challenge and contribute a Cl K-edge X-ray absorption spectroscopy and relativistic density functional theory study that quantitatively evaluates An–Cl covalency in AnCl62– (AnIV = Th, U, Np, Pu). Lastly, the results showed significant mixing between Cl 3p- and AnIV 5f- and 6d-orbitals (t1u*/t2u* and t2g*/eg*), with the 6d-orbitals showing more pronounced covalent bonding than the 5f-orbitals. Moving from Th to U, Np, and Pu markedly changed the amount of M–Cl orbital mixing, such that AnIV 6d- and Cl 3p-mixing decreased and metal 5f- and Cl 3p-orbital mixing increased across this series.
Su, Jing, et al. "Energy-Degeneracy-Driven Covalency in Actinide Bonding." Journal of the American Chemical Society, vol. 140, no. 51, Dec. 2018. https://doi.org/10.1021/jacs.8b09436
Su, Jing, Batista, Enrique Ricardo, Boland, Kevin Sean, Bone, Sharon E., Bradley, Joseph A., Cary, Samantha K., Clark, David Lewis, Conradson, Steven Daniel, Ditter, Alexander Scott, Kaltsoyannis, Nikolas, Keith, Jason M., Kerridge, Andrew, Kozimor, Stosh Anthony, Loeble, Matthias W., Martin, Richard L., Minasian, Stefan G., Mocko, Veronika, La Pierre, Henry S., ... Yang, Ping (2018). Energy-Degeneracy-Driven Covalency in Actinide Bonding. Journal of the American Chemical Society, 140(51). https://doi.org/10.1021/jacs.8b09436
Su, Jing, Batista, Enrique Ricardo, Boland, Kevin Sean, et al., "Energy-Degeneracy-Driven Covalency in Actinide Bonding," Journal of the American Chemical Society 140, no. 51 (2018), https://doi.org/10.1021/jacs.8b09436
@article{osti_1489963,
author = {Su, Jing and Batista, Enrique Ricardo and Boland, Kevin Sean and Bone, Sharon E. and Bradley, Joseph A. and Cary, Samantha K. and Clark, David Lewis and Conradson, Steven Daniel and Ditter, Alexander Scott and Kaltsoyannis, Nikolas and others},
title = {Energy-Degeneracy-Driven Covalency in Actinide Bonding},
annote = {Evaluating the nature of chemical bonding for actinide elements represents one of the most important and long-standing problems in actinide science. In this work, we directly address this challenge and contribute a Cl K-edge X-ray absorption spectroscopy and relativistic density functional theory study that quantitatively evaluates An–Cl covalency in AnCl62– (AnIV = Th, U, Np, Pu). Lastly, the results showed significant mixing between Cl 3p- and AnIV 5f- and 6d-orbitals (t1u*/t2u* and t2g*/eg*), with the 6d-orbitals showing more pronounced covalent bonding than the 5f-orbitals. Moving from Th to U, Np, and Pu markedly changed the amount of M–Cl orbital mixing, such that AnIV 6d- and Cl 3p-mixing decreased and metal 5f- and Cl 3p-orbital mixing increased across this series.},
doi = {10.1021/jacs.8b09436},
url = {https://www.osti.gov/biblio/1489963},
journal = {Journal of the American Chemical Society},
issn = {ISSN 0002-7863},
number = {51},
volume = {140},
place = {United States},
publisher = {American Chemical Society (ACS)},
year = {2018},
month = {12}}