Theoretical examination of covalency in berkelium(IV) carbonate complexes
Abstract
Abstract Experimental studies on the speciation of berkelium in carbonate media have shown that complexation of berkelium(III) by carbonate results in spontaneous oxidation to berkelium(IV) and that multiple species can be present in solution. We studied two proposed structures present in solution based on theoretical comparisons with spectroscopic data previously reported for Bk(IV) carbonate solutions. The multiconfigurational character of the ground and low‐lying excited states in both complexes is demonstrated to result from the strong spin‐orbit coupling. Although bonding in Bk(IV) carbonate and carbonate‐hydroxide complexes is dominated by strong Coulombic forces, the presence of non‐negligible covalent character is supported by ligand‐field theory, natural localized orbitals, topological studies of the electron density, and energy transition state natural orbitals for chemical valence. Bond orders based on natural localized molecular orbitals show that BkOH bonds possess enhanced orbital overlap, which is reflected in the bond strength. This is also observed in the decomposition of the orbital interaction energy into individual deformation density pairs.
- Authors:
-
[1];
[2];
[1]
- Florida State Univ., Tallahassee, FL (United States)
- Universidad Andres Bello (Chile)
- Publication Date:
- Research Org.:
- Florida State Univ., Tallahassee, FL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1802141
- Alternate Identifier(s):
- OSTI ID: 1615952
- Grant/Contract Number:
- SC0010677; DE‐FG02‐13ER16414
- Resource Type:
- Accepted Manuscript
- Journal Name:
- International Journal of Quantum Chemistry
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 15; Journal ID: ISSN 0020-7608
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Mathematics; Physics; Actinides; CASSCF; NLMO; Relativistic effects; Electronic structure; Bonding; Ligand-field theory
Citation Formats
Albrecht‐Schmitt, Thomas E., Hobart, David E., Páez‐Hernández, Dayan, and Celis‐Barros, Cristian. Theoretical examination of covalency in berkelium(IV) carbonate complexes. United States: N. p., 2020.
Web. doi:10.1002/qua.26254.
Albrecht‐Schmitt, Thomas E., Hobart, David E., Páez‐Hernández, Dayan, & Celis‐Barros, Cristian. Theoretical examination of covalency in berkelium(IV) carbonate complexes. United States. https://doi.org/10.1002/qua.26254
Albrecht‐Schmitt, Thomas E., Hobart, David E., Páez‐Hernández, Dayan, and Celis‐Barros, Cristian. Thu .
"Theoretical examination of covalency in berkelium(IV) carbonate complexes". United States. https://doi.org/10.1002/qua.26254. https://www.osti.gov/servlets/purl/1802141.
@article{osti_1802141,
title = {Theoretical examination of covalency in berkelium(IV) carbonate complexes},
author = {Albrecht‐Schmitt, Thomas E. and Hobart, David E. and Páez‐Hernández, Dayan and Celis‐Barros, Cristian},
abstractNote = {Abstract Experimental studies on the speciation of berkelium in carbonate media have shown that complexation of berkelium(III) by carbonate results in spontaneous oxidation to berkelium(IV) and that multiple species can be present in solution. We studied two proposed structures present in solution based on theoretical comparisons with spectroscopic data previously reported for Bk(IV) carbonate solutions. The multiconfigurational character of the ground and low‐lying excited states in both complexes is demonstrated to result from the strong spin‐orbit coupling. Although bonding in Bk(IV) carbonate and carbonate‐hydroxide complexes is dominated by strong Coulombic forces, the presence of non‐negligible covalent character is supported by ligand‐field theory, natural localized orbitals, topological studies of the electron density, and energy transition state natural orbitals for chemical valence. Bond orders based on natural localized molecular orbitals show that BkOH bonds possess enhanced orbital overlap, which is reflected in the bond strength. This is also observed in the decomposition of the orbital interaction energy into individual deformation density pairs.},
doi = {10.1002/qua.26254},
journal = {International Journal of Quantum Chemistry},
number = 15,
volume = 120,
place = {United States},
year = {Thu Apr 23 00:00:00 EDT 2020},
month = {Thu Apr 23 00:00:00 EDT 2020}
}
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