Jump to main content
Jump to site search

Issue 2, 2016
Previous Article Next Article

First structural characterization of Pa(iv) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(iv): the evidence of a curium break

Author affiliations

Abstract

More than a century after its discovery the structure of the Pa4+ ion in acidic aqueous solution has been investigated for the first time experimentally and by quantum chemistry. The combined results of EXAFS data and quantum chemically optimized structures suggest that the Pa4+ aqua ion has an average of nine water molecules in its first hydration sphere at a mean Pa–O distance of 2.43 Å. The data available for the early tetravalent actinide (An) elements from Th4+ to Bk4+ show that the An–O bonds have a pronounced electrostatic character, with bond distances following the same monotonic decreasing trend as the An4+ ionic radii, with a decrease of the hydration number from nine to eight for the heaviest ions Cm4+ and Bk4+. Being the first open-shell tetravalent actinide, Pa4+ features a coordination chemistry very similar to its successors. The electronic configuration of all open-shell systems corresponds to occupation of the valence 5f orbitals, without contribution from the 6d orbitals. Our results thus demonstrate that Pa(IV) resembles its early actinide neighbors.

Graphical abstract: First structural characterization of Pa(iv) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(iv): the evidence of a curium break

  • This article is part of the themed collection: HOT Articles
Back to tab navigation

Supplementary files

Publication details

The article was received on 11 Sep 2015, accepted on 06 Oct 2015 and first published on 08 Oct 2015


Article type: Communication
DOI: 10.1039/C5DT03560K
Author version
available:
Download author version (PDF)
Dalton Trans., 2016,45, 453-457

  •   Request permissions

    First structural characterization of Pa(IV) in aqueous solution and quantum chemical investigations of the tetravalent actinides up to Bk(IV): the evidence of a curium break

    N. L. Banik, V. Vallet, F. Réal, R. M. Belmecheri, B. Schimmelpfennig, J. Rothe, R. Marsac, P. Lindqvist-Reis, C. Walther, M. A. Denecke and C. M. Marquardt, Dalton Trans., 2016, 45, 453
    DOI: 10.1039/C5DT03560K

Search articles by author

Spotlight

Advertisements