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Ionic Crystal Structures

Ionic Crystal Structures

Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
Most monatomic ions behave as charged spheres, and their attraction for ions of opposite charge is the same in every direction. Consequently, stable structures for ionic compounds result (1) when ions of one charge are surrounded by as many ions as possible of the opposite...

Metallic Solids

Metallic Solids

Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many...

Coordination Number and Geometry

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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.

Crystal Field Theory - Octahedral Complexes

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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...

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Tetrahedral Complexes
Crystal field theory (CFT) is applicable to molecules in geometries other than octahedral. In octahedral complexes, the lobes of the dx2−y2 and dz2 orbitals point directly at the ligands. For tetrahedral complexes, the d orbitals remain in place, but with only four ligands located between the axes. None of the orbitals points directly at the tetrahedral ligands. However, the dx2−y2 and dz2 orbitals (along the Cartesian axes) overlap with the ligands less than the dxy,...

Valence Bond Theory

Valence Bond Theory

Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...

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Synthesis, Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

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Hollow polyhedral structures in small gold-sulfide clusters.

Yong Pei¹, Nan Shao, Hui Li

¹Department of Chemistry and Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, Lincoln, Nebraska 68588, USA.

|January 29, 2011

Summary

This summary is machine-generated.

Gold-sulfide cluster anions exhibit simple size-evolution rules and novel hollow polyhedron structures. A 3:2 gold/sulfur ratio is key for forming these stable, cage-like gold-sulfide nanostructures.

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Area of Science:

* Computational chemistry and materials science.
* Nanotechnology and cluster physics.

Background:

* Understanding the structural properties of gold-sulfide clusters is crucial for designing new nanomaterials.
* Previous experimental studies have identified specific gold-sulfide cluster stoichiometries.

Purpose of the Study:

* To investigate the structural evolution of gold-sulfide cluster anions (Au(m)S(n)(-)) using theoretical methods.
* To identify simple rules governing cluster growth and the formation of novel structures.
* To explain the stability of observed gold-sulfide species.

Main Methods:

* Ab initio computational methods were employed to simulate and analyze cluster structures.
* Analysis of structural evolution based on size and stoichiometry.
* Comparison with experimental data from ion mobility mass spectrometry.

Main Results:

* Gold-sulfide cluster anions display predictable size-evolution patterns.
* Novel hollow polyhedron structures were discovered, including quasi-tetrahedron, pyramidal, quasi-triangular prism, and quasi-cuboctahedron geometries.
* The stability of the S-Au-S unit and a 3:2 gold/sulfur ratio are critical for polyhedron formation.
* A unique "edge-to-face" growth mechanism was proposed for small clusters.

Conclusions:

* Gold-sulfide clusters follow simple rules for structural development.
* Hollow polyhedron structures are a common motif in stable gold-sulfide anions.
* The 3:2 Au/S ratio is a significant indicator for the formation of these stable, hollow structures.