Lanthanide and Actinide Chemistry

Cotton, S. A.

doi:10.1002/0470010088

Cited by 872 publications

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“…Interestingly, the analogous cubic {RuPr 3 }X 3 (X = Br, I) systems 10,12,18 form the monoclinic structure, as expected by the electronic structure. Although calculations on {RuPr 3 }Br 3 have not been reported, it is likely that Pr and La will have the same structural preferences because of similar features of their valence electronic states 53 and form the monoclinic structure, which is in agreement with experimental observations. 10 Additionally, the analogous Os-containing compound, that is, {OsPr 3 }I 3 , has been reported to crystallize in both structure types 9,13 and, thus, demonstrates the complexity and electronic subtleties of the {TnR 3 }X 3 system (Table 5).…”

Section: Resultssupporting

confidence: 82%

Identifying a Structural Preference in Reduced Rare-Earth Metal Halides by Combining Experimental and Computational Techniques

et al. 2012

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The structures of two new cubic {TnLa 3 }Br 3 (Tn = Ru, Ir; I4 1 32, Z = 8; Tn = Ru: a = 12.1247(16) Å, V = 1782.4(4) Å 3 ; Tn = Ir: a = 12.1738(19) Å, V = 1804.2(5) Å 3 ) compounds belonging to a family of reduced rare-earth metal halides were determined by single-crystal X-ray diffraction. Interestingly, the isoelectronic compound {RuLa 3 }I 3 crystallizes in the monoclinic modification of the {TnR 3 }X 3 family, while {IrLa 3 }I 3 was found to be isomorphous with cubic {PtPr 3 }I 3 . Using electronic structure calculations, a pseudogap was identified at the Fermi level of {IrLa 3 }Br 3 in the new cubic structure. Additionally, the structure attempts to optimize (chemical) bonding as determined through the crystal orbital Hamilton populations (COHP) curves. The Fermi level of the isostructural {RuLa 3 }Br 3 falls below the pseudogap, yet the cubic structure is still formed. In this context, a close inspection of the distinct bond frequencies reveals the subtleness of the structure determining factors. ABSTRACT: The structures of two new cubic {TnLa 3 }Br 3 (Tn = Ru, Ir; I4 1 32, Z = 8; Tn = Ru: a = 12.1247(16) Å, V = 1782.4(4) Å 3 ; Tn = Ir: a = 12.1738(19) Å, V = 1804.2(5) Å 3 ) compounds belonging to a family of reduced rare-earth metal halides were determined by single-crystal X-ray diffraction. Interestingly, the isoelectronic compound {RuLa 3 }I 3 crystallizes in the monoclinic modification of the {TnR 3 }X 3 family, while {IrLa 3 }I 3 was found to be isomorphous with cubic {PtPr 3 }I 3 . Using electronic structure calculations, a pseudogap was identified at the Fermi level of {IrLa 3 }Br 3 in the new cubic structure. Additionally, the structure attempts to optimize (chemical) bonding as determined through the crystal orbital Hamilton populations (COHP) curves. The Fermi level of the isostructural {RuLa 3 }Br 3 falls below the pseudogap, yet the cubic structure is still formed. In this context, a close inspection of the distinct bond frequencies reveals the subtleness of the structure determining factors.

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Section: Resultssupporting

confidence: 82%

Identifying a Structural Preference in Reduced Rare-Earth Metal Halides by Combining Experimental and Computational Techniques

et al. 2012

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“…[7] The AnO 2 + oxidation states assigned here are showni nT able 4a long with the known (and proposed)actinideoxidationstates. [25][26][27][28][29][30][31] Naturalpopulation analysis (NPA)…”

Section: Computed Structures and Energetics Of Ano 2 + + Cationsmentioning

confidence: 99%

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

Dau

Vasiliu

Peterson

et al. 2017

Chemistry A European J

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“…in references [133][134][135]. The RTAM searchable database [136] also includes an up-to-date list of relativistic calculations for atoms and molecules.…”

Section: Some Aspects Of Relativistic Quantum Chemistrymentioning

confidence: 99%

Electronic structure theory to decipher the chemical bonding in actinide systems

Dognon

2017

Coordination Chemistry Reviews

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International audienceThe chemical bonding in actinide compounds is usually analysed by inspecting the shape and the occupation of the orbitals or by calculating bond orders which are based on orbital overlap and occupation numbers. However, this may not give a definite answer because the choice of the partitioning method may strongly influence the result possibly leading to qualitatively different answers. In this review, we summarized the state-of-the-art of methods dedicated to the theoretical characterisation of bonding including charge, orbital, quantum chemical topology and energy decomposition analyses. This review is not exhaustive but aims to highlight some of the ways opened up by recent methodological developments. Various examples have been chosen to illustrate this progress

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Lanthanide and Actinide Chemistry

Cited by 872 publications

References 0 publications

Identifying a Structural Preference in Reduced Rare-Earth Metal Halides by Combining Experimental and Computational Techniques

Identifying a Structural Preference in Reduced Rare-Earth Metal Halides by Combining Experimental and Computational Techniques

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

Electronic structure theory to decipher the chemical bonding in actinide systems

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