Curvature of the lanthanide contraction: An explanation

Raymond, Kenneth N.; Wellman, Daniel L.; Sgarlata, Carmelo; Hill, Aru P.

doi:10.1016/j.crci.2010.03.034

Cited by 32 publications

(31 citation statements)

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“…The contraction along the lanthanide series has been reported as quadratic by Quadrelli (2002); this was confirmed by Seitz et al (2007) for an isostructural series of trivalent La-Lu complexes (R 2 > 0.99); they also showed that the relation may be derived theoretically from Slater's model of atomic shielding constants (Slater, 1930). This was expanded by Raymond et al (2010) using hydrogen-type wavefunctions. We verify these results below.…”

Section: Research Papersmentioning

confidence: 66%

“…The curvature of the lanthanide contraction for trivalent ions has been investigated by Quadrelli (2002), Seitz et al (2007) and Raymond et al (2010). Quadrelli (2002) gave the mean bond length of the three equatorial bonds and that of the six other bonds as a function of the number of electrons in the f shell for a series of isotypical compounds in which the lanthanide ions are [9]-coordinated.…”

Section: Observed F-block Contraction For Cations Bonded To O 2àmentioning

confidence: 99%

“…Seitz et al (2007) gave the sum of all Ln-O bonds (Ln = lanthanide) as a function of the number of electrons in the f shell for a different series of isotypical compounds of the Ln ions with coordination number [8]. Raymond et al (2010) gave the inverse of the ionic radius as a function of the number of f electrons in different lanthanide complexes and obtained a linear correlation. Our data show a nearly identical fit whether we plot mean bond length or the inverse of ionic radius as a function of the number of f electrons; however, the relation of Raymond et al (2010) has the advantage of being linear, whereas those of Quadrelli (2002) and Seitz et al (2007) are quadratic.…”

Section: Observed F-block Contraction For Cations Bonded To O 2àmentioning

confidence: 99%

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Bond-length distributions for ions bonded to oxygen: results for the lanthanides and actinides and discussion of the f-block contraction

Gagné

2018

Acta Crystallogr B Struct Sci Cryst Eng Mater

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Bond-length distributions have been examined for 84 configurations of the lanthanide ions and 22 configurations of the actinide ions bonded to oxygen, for 1317 coordination polyhedra and 10 700 bond distances for the lanthanide ions, and 671 coordination polyhedra and 4754 bond distances for the actinide ions. A linear correlation between mean bond length and coordination number is observed for the trivalent lanthanides ions bonded to O 2À . The lanthanide contraction for the trivalent lanthanide ions bonded to O 2À is shown to vary as a function of coordination number, and to diminish in scale with an increasing coordination number. The decrease in mean bond length from La 3+ to Lu 3+ is 0.25 Å for coordination number (CN) 6 (9.8%), 0.22 Å for CN 7 (8.7%), 0.21 Å for CN 8 (8.0%), 0.21 Å for CN 9 (8.2%) and 0.18 Å for CN 10 (6.9%). The crystal chemistry of Np 5+ and Np 6+ is shown to be very similar to that of U 6+ when bonded to O 2À , but differs for Np 7+ . research papers 60 Olivier C. Gagné Bond-length distributions for ions bonded to oxygen Acta Cryst. (2018). B74, 49-62 Figure 10 Bond-length distributions for (a) [2+2+4]-coordination, (b) [2+6]coordination and (c) the aggregate of (a) and (b) for U 6+ O 8 polyhedra.

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Section: Research Papersmentioning

confidence: 66%

Section: Observed F-block Contraction For Cations Bonded To O 2àmentioning

confidence: 99%

Section: Observed F-block Contraction For Cations Bonded To O 2àmentioning

confidence: 99%

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Bond-length distributions for ions bonded to oxygen: results for the lanthanides and actinides and discussion of the f-block contraction

Gagné

2018

Acta Crystallogr B Struct Sci Cryst Eng Mater

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“…Raymond et al 2010). This results in a systematic variation of speciation in seawater dominated by complexes with carbonate ions (Chantrell and Byre, 1987).…”

Section: Introductionmentioning

confidence: 99%

Rare earth element distribution in the Atlantic sector of the Southern Ocean: The balance between particle scavenging and vertical supply

et al. 2015

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The concentrations of rare earth elements (REEs) in seawater display systematic variations related to weathering inputs, particle scavenging and water mass histories.Here we investigate the REE concentrations of water column profiles in the Atlantic sector of the Southern Ocean, a key region of the global circulation and primary production. The data reveal a pronounced contrast between the vertical profiles in the

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“…Under typical geological conditions they occur as trivalent cations with the exception of Ce (also often tetravalent) and Eu (often also divalent). Their valence electron structures are similar, and cationic radii vary quadratically from the large La 3+ to the small Lu 3+ due to the lanthanide contraction (Raymond et al , 2010; Seitz et al , 2007). This contraction, together with its effect on mesoscale molecular interactions (Ferru et al , 2016) leads to small yet gradual and predictable changes in their chemical behaviour.…”

Section: Introductionmentioning

confidence: 99%

Rare earth mineral diversity controlled by REE pattern shapes

Anenburg

2020

MinMag

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The line connecting rare earth elements (REE) in chondrite-normalised plots can be represented by a smooth polynomial function using λ shape coefficients as described by O'Neill (2016). In this study, computationally generated λ combinations are used to construct artificial chondrite-normalised REE patterns that encompass most REE patterns likely to occur in natural materials. The dominant REE per pattern is identified, which would lead to its inclusion in a hypothetical mineral suffix, had this mineral contained essential REE. Furthermore, negative Ce and Y anomalies, common in natural minerals, are considered in the modelled REE patterns to investigate the effect of their exclusion on the relative abundance of the remainder REE. The dominant REE in a mineral results from distinct pattern shapes requiring specific fractionation processes, thus providing information on its genesis. Minerals dominated by heavy lanthanides are rare or non-existent, even though the present analysis shows that REE patterns dominated by Gd, Dy, Er and Yb are geologically plausible. This discrepancy is caused by the inclusion of Y, which dominates heavy REE budgets, in mineral name suffixes. The focus on Y obscures heavy lanthanide mineral diversity and can lead to various fractionation processes to be overlooked. Samarium dominant minerals are known, even though deemed unlikely by the computational model, suggesting additional fractionation processes that are not well described by λ shape coefficients. Positive Eu anomalies only need to be moderate in minerals depleted in the light REE for Eu to be the dominant REE, thus identifying candidate rocks in which the first Eu dominant mineral might be found. Here, I present an online tool, called ALambdaR that allows interactive control of λ shape coefficients and visualisation of resulting REE patterns.

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Curvature of the lanthanide contraction: An explanation

Abstract: This is an electronic version of an article published in Comptes Rendus Chimie. 2010, 13, 849-852 This is an electronic version of an article published in Comptes Rendus Chimie. 2010, 13, 849-852. Comptes Rendus Chime is available online at: http://dx.doi.org

Cited by 32 publications

References 20 publications

Bond-length distributions for ions bonded to oxygen: results for the lanthanides and actinides and discussion of the f-block contraction

Bond-length distributions for ions bonded to oxygen: results for the lanthanides and actinides and discussion of the f-block contraction

Rare earth element distribution in the Atlantic sector of the Southern Ocean: The balance between particle scavenging and vertical supply

Rare earth mineral diversity controlled by REE pattern shapes

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