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Bismuth Polycations
Bismuth polycations are polyatomic ions of the formula . They were originally observed in solutions of bismuth metal in molten bismuth chloride. It has since been found that these clusters are present in the solid state, particularly in salts where germanium tetrachloride or tetrachloroaluminate serve as the counteranions, but also in amorphous phases such as glasses and gels. Bismuth endows materials with a variety of interesting optical properties that can be tuned by changing the supporting material. Commonly-reported structures include the trigonal bipyramidal cluster, the octahedral cluster, the square antiprismatic cluster, and the tricapped trigonal prismatic cluster. Known materials Crystalline * Bi5(AlCl4)3 * Bi8(AlCl4)2 * Bi5(GaCl4)3 * Bi8(GaCl4)2 Metal complexes * uBi8AlCl4]3 * u(Bi8)2sup>6+ * u2Bi14Br4AlCl4]4 Structure and bonding Bismuth polycations form despite the fact that they possess fewer total valence electrons than would seem necessary for the ...
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Wade's Rules
In chemistry the polyhedral skeletal electron pair theory (PSEPT) provides electron counting rules useful for predicting the structures of cluster compound, clusters such as borane and carborane clusters. The electron counting rules were originally formulated by Kenneth Wade, and were further developed by others including Michael Mingos; they are sometimes known as Wade's rules or the Wade–Mingos rules. The rules are based on a molecular orbital treatment of the bonding. These notes contained original material that served as the basis of the sections on the 4''n'', 5''n'', and 6''n'' rules. These rules have been extended and unified in the form of the Jemmis mno rules, Jemmis ''mno'' rules. Predicting structures of cluster compounds Different rules (4''n'', 5''n'', or 6''n'') are invoked depending on the number of electrons per vertex. The 4''n'' rules are reasonably accurate in predicting the structures of clusters having about 4 electrons per vertex, as is the case for many ...
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Bismuth Compounds
Bismuth compounds are compounds containing the element bismuth (Bi). Bismuth forms trivalent and pentavalent compounds, the trivalent ones being more common. Many of its chemical properties are similar to those of arsenic and antimony, although they are less toxic than derivatives of those lighter elements. Oxides and sulfides At elevated temperatures, the vapors of the metal combine rapidly with oxygen, forming the yellow trioxide, . Wiberg, p. 768. Greenwood, p. 553. When molten, at temperatures above 710 °C, this oxide corrodes any metal oxide and even platinum. Krüger, p. 185 On reaction with a base, it forms two series of oxyanions: , which is polymeric and forms linear chains, and . The anion in is a cubic octameric anion, , whereas the anion in is tetrameric. The dark red bismuth(V) oxide, , is unstable, liberating gas upon heating. The compound NaBiO3 is a strong oxidising agent. Greenwood, p. 578. Bismuth sulfide, , occurs naturally in bismuth ores. It i ...
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Near-infrared Window In Biological Tissue
The near-infrared (NIR) window (also known as optical window or therapeutic window) defines the range of wavelengths from 650 to 1350 nanometre (nm) where light has its maximum depth of penetration in tissue. Within the NIR window, scattering is the most dominant light-tissue interaction, and therefore the propagating light becomes diffused rapidly. Since scattering increases the distance travelled by photons within tissue, the probability of photon absorption also increases. Because scattering has weak dependence on wavelength, the NIR window is primarily limited by the light absorption of blood at short wavelengths and water at long wavelengths. The technique using this window is called NIRS. Medical imaging techniques such as fluorescence image-guided surgery often make use of the NIR window to detect deep structures. Absorption properties of tissue components The absorption coefficient (\mu_) is defined as the probability of photon absorption in tissue per unit path length. D ...
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Near Infrared Optical Tomography
Medical optical imaging is the use of light as an investigational imaging technique for medical applications. Examples include optical microscopy, spectroscopy, endoscopy, scanning laser ophthalmoscopy, laser Doppler imaging, and optical coherence tomography. Because light is an electromagnetic wave, similar phenomena occur in X-rays, microwaves, and radio waves. Optical imaging systems may be divided into diffusive and ballistic imaging systems. A model for photon migration in turbid biological media has been developed by Bonner et al. Such a model can be applied for interpretation data obtained from laser Doppler blood-flow monitors and for designing protocols for therapeutic excitation of tissue chromophores. Diffusive optical imaging Diffuse optical imaging (DOI) is a method of imaging using near-infrared spectroscopy (NIRS) or fluorescence-based methods. When used to create 3D volumetric models of the imaged material DOI is referred to as diffuse optical tomography, whereas ...
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HOMO/LUMO
In chemistry, HOMO and LUMO are types of molecular orbitals. The acronyms stand for ''highest occupied molecular orbital'' and ''lowest unoccupied molecular orbital'', respectively. HOMO and LUMO are sometimes collectively called the ''frontier orbitals'', such as in the frontier molecular orbital theory. Gap The energy difference between the HOMO and LUMO is ''the HOMO–LUMO gap''. Its size can be used to predict the strength and stability of transition metal complexes, as well as the colors they produce in solution.Griffith, J. S. and L. E. Orgel"Ligand Field Theory" ''Q. Rev. Chem. Soc.'' 1957, 11, 381–383. As a rule of thumb, the larger a compound's HOMO-LUMO gap, the more stable the compound. Semiconductors The HOMO level is to organic semiconductors roughly what the maximum valence band is to inorganic semiconductors and quantum dots. The same analogy can be made between the LUMO level and the conduction band minimum.Bredas, J,-L"Mind the gap!" ''Mater. Horiz.'' 201 ...
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Ligand
In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection requires critical consideration in many practical areas, including bioinorganic and medicinal chemistry, homogeneous catalysis, and environmental chemi ...
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Three-center Two-electron Bond
A three-center two-electron (3c–2e) bond is an electron-deficient chemical bond where three atoms share two electrons. The combination of three atomic orbitals form three molecular orbitals: one bonding, one ''non''-bonding, and one ''anti''-bonding. The two electrons go into the bonding orbital, resulting in a net bonding effect and constituting a chemical bond among all three atoms. In many common bonds of this type, the bonding orbital is shifted towards two of the three atoms instead of being spread equally among all three. Example molecules with 3c–2e bonds are the trihydrogen cation () and diborane (). In these two structures, the three atoms in each 3c-2e bond form an angular geometry, leading to a bent bond. Boranes and carboranes An extended version of the 3c–2e bond model features heavily in cluster compounds described by the polyhedral skeletal electron pair theory, such as boranes and carboranes. These molecules derive their stability from having a completel ...
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Molecular Orbital
In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding an electron in any specific region. The terms ''atomic orbital'' and ''molecular orbital'' were introduced by Robert S. Mulliken in 1932 to mean ''one-electron orbital wave functions''. At an elementary level, they are used to describe the ''region'' of space in which a function has a significant amplitude. In an isolated atom, the orbital electrons' location is determined by functions called atomic orbitals. When multiple atoms combine chemically into a molecule, the electrons' locations are determined by the molecule as a whole, so the atomic orbitals combine to form molecular orbitals. The electrons from the constituent atoms occupy the molecular orbitals. Mathematically, molecular orbitals are an approximate solution to the Schrödin ...
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Sigma Bond
In chemistry, sigma bonds (σ bonds) are the strongest type of covalent chemical bond. They are formed by head-on overlapping between atomic orbitals. Sigma bonding is most simply defined for diatomic molecules using the language and tools of symmetry groups. In this formal approach, a σ-bond is symmetrical with respect to rotation about the bond axis. By this definition, common forms of sigma bonds are s+s, pz+pz, s+pz and dz2+dz2 (where z is defined as the axis of the bond or the internuclear axis). Quantum theory also indicates that molecular orbitals (MO) of identical symmetry actually mix or ''hybridize''. As a practical consequence of this mixing of diatomic molecules, the wavefunctions s+s and pz+pz molecular orbitals become blended. The extent of this mixing (or hybridization or blending) depends on the relative energies of the MOs of like symmetry. For homodiatomics (homonuclear diatomic molecules), bonding σ orbitals have no nodal planes at which the wavefunction i ...
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Polyatomic Ion
A polyatomic ion, also known as a molecular ion, is a covalent bonded set of two or more atoms, or of a metal complex, that can be considered to behave as a single unit and that has a net charge that is not zero. The term molecule may or may not be used to refer to a polyatomic ion, depending on the definition used. The prefix ''poly-'' carries the meaning "many" in Greek, but even ions of two atoms are commonly described as polyatomic. In older literature, a polyatomic ion may instead be referred to as a ''radical'' (or less commonly, as a ''radical group''). In contemporary usage, the term ''radical'' refers to various free radicals, which are species that have an unpaired electron and need not be charged. A simple example of a polyatomic ion is the hydroxide ion, which consists of one oxygen atom and one hydrogen atom, jointly carrying a net charge of −1; its chemical formula is . In contrast, an ammonium ion consists of one nitrogen atom and four hydrogen atoms, with a ch ...
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