Principles Determining the Structure of Transition Metals

For the better part of a century researchers across disciplines have sought to explain the crystallography of the elemental transition metals: hexagonal close packed, body centered cubic, and face centered cubic in a form similar to that used to rationalize the structure of organic molecules and ino...

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Bibliographic Details
Published in:Molecules (Basel, Switzerland) Switzerland), 2021-09, Vol.26 (17), p.5396
Main Authors: Riddle, Samuel K, Wilson, Timothy R, Rajivmoorthy, Malavikha, Eberhart, Mark E
Format: Article
Language:English
Subjects:
BCC metals
Charge transfer
Chemical reactions
Chemists
Computational chemistry
Crystal structure
Crystallography
Electron density
frontier orbital theory
Investigations
Kinetic energy
Metallurgy
Metals
Molecular chemistry
Molecular structure
Organic chemistry
quantum theory of atoms in molecules
transition metal structure
Transition metals
Trends
viral theorem
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Summary:For the better part of a century researchers across disciplines have sought to explain the crystallography of the elemental transition metals: hexagonal close packed, body centered cubic, and face centered cubic in a form similar to that used to rationalize the structure of organic molecules and inorganic complexes. Pauling himself tried with limited success to address the origins of transition metal stability. These early investigators were handicapped, however, by incomplete knowledge regarding the structure of metallic electron density. Here, we exploit modern approaches to electron density analysis to first comprehensively describe transition metal electron density. Then, we use topological partitioning and quantum mechanically rigorous treatments of kinetic energy to account for the structure of the density as arising from the interactions between metallic polyhedra. We argue that the crystallography of the early transition metals results from charge transfer from the so called "octahedral" to "tetrahedral cages" while the face centered cubic structure of the late transition metals is a consequence of anti-bonding interactions that increase octahedral hole kinetic energy.
ISSN:1420-3049
1420-3049
DOI:10.3390/molecules26175396