Theoretical examination of covalency in berkelium(IV) carbonate complexes

Thomas E. Albrecht-Schmitt, David E. Hobart, Dayan Páez-Hernández, Cristian Celis-Barros

Resultado de la investigación: Contribución a una revistaArtículorevisión exhaustiva

3 Citas (Scopus)

Resumen

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 BkOH 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.

Idioma originalInglés
Número de artículoe26254
PublicaciónInternational Journal of Quantum Chemistry
Volumen120
N.º15
DOI
EstadoEn prensa - 1 ene 2020

Áreas temáticas de ASJC Scopus

  • Óptica y física atómica y molecular
  • Física de la materia condensada
  • Química física y teórica

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