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 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.

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 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 charge density. Here we exploit modern approaches to charge analysis to first comprehensively describe transition metal charge 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 tetrahedra. We argue that the crystallography of the early transition metals results from charge transfer from the so called “octahedral” to “tetrahedral holes” while the face centered cubic structure of the late transition metals is a consequence of antibonding interactions that increase octahedral hole kinetic energy.

Speciation of Inorganic Compounds in Aquatic Systems Using Diffusive Gradients in Thin-Films: A Review

The speciation of trace metals in an aquatic system involves the determination of free ions, complexes (labile and non-labile), colloids, and the total dissolved concentration. In this paper, we review the integrated assessment of free ions and labile metal complexes using Diffusive Gradients in Thin-films (DGT), a dynamic speciation technique. The device consists of a diffusive hydrogel layer made of polyacrylamide, backed by a layer of resin (usually Chelex-100) for all trace metals except for Hg. The best results for Hg speciation are obtained with agarose as hydrogel and a thiol-based resin. The diffusive domain controls the diffusion flux of the metal ions and complexes to the resin, which strongly binds all free ions. By using DGT devices with different thicknesses of the diffusive or resin gels and exploiting expressions derived from kinetic models, one can determine the labile concentrations, mobilities, and labilities of different species of an element in an aquatic system. This procedure has been applied to the determination of the organic pool of trace metals in freshwaters or to the characterization of organic and inorganic complexes in sea waters. The concentrations that are obtained represent time-weighted averages (TWA) over the deployment period.

Investigation of the inhibitory-bactericidal effect of amidoamine-based inorganic complexes against microbiological and atmospheric corrosion

In the process, inorganic complexes of amidoamines obtained from the interaction of natural petroleum acid and oleic acids with diethylenetriamine have been developed and their effectiveness as inhibitor-bactericides has been investigated. The effect of the synthesized reagents on the kinetics of the corrosion process of steel and the activity of sulphate-reducing bacteria in 3% NaCl solution saturated with CO2 and in the biphasic water–isopropyl alcohol medium with H2S dissolved has been analyzed. The thermodynamic and kinetic parameters of the corrosion process were calculated. The adsorption of the complexes was investigated using the Langmuir isotherm and the correlation constant was determined. State of the metal surface was investigated by SEM method in CO2 and H2S media, with and without inhibitors, and the metal surface contact of complexes was studied by computer molecular simulation.

Enumeration of de novo inorganic complexes for chemical discovery and machine learning

Enumerated, de novo transition metal complexes have unique spin state properties and accelerate machine learning model training.

Bismuth triiodide complexes: structure, spectroscopy, electronic properties, and memristive properties

A clockwise and anticlockwise I–V pattern observed for memristive devices based on bismuth(iii) iodide organic–inorganic complexes and different metal electrodes.