The “Coloring Problem” in Solids: How It Affects Structure, Composition and Properties

Miller, Gordon J.

doi:10.1002/(sici)1099-0682(199805)1998:5<523::aid-ejic523>3.0.co;2-l

Cited by 228 publications

(240 citation statements)

References 80 publications

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“…Due to the cation disorder (and the large unit cell, which does not allow to calculate ordered superstructures), two model compounds K 16 Ga 47 In 8 (with all six potassium positions fully occupied) and K 14 Ga 47 In 8 [without K(6)] were set up for the DFT band structure calculations, whereby one should be aware that the first model is one potassium cation (i.e. one electron/ f.u.)…”

Section: Electronic Structure Chemical Bonding and "Coloring" Aspectsmentioning

confidence: 99%

“…Similarly, the atoms of the [M 13 ] cluster, which are coordinated by up to five cations are more negative than the icosahedra-forming Ga with their threefold K + coordination. In contrast to ternary polar alkali/alkaline earth intermetallics with a significant polarity inside the polyanion, in which the preference of heteroatomic bonds determines the "coloring" of the polyanion, [16,43] the small difference in electronegativity between Ga and In in the title compound implies that space requirements of the different atomic positions are the dominating factor for the Ga/In distribution in the polyanion.…”

mentioning

confidence: 99%

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The New Mixed Cluster Trielide K₃Ga_11–xIn_x (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

Falk

Meyer

Röhr

2017

Zeitschrift anorg allge chemie

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Abstract. The new cluster compound K 3 Ga 11-x In x , which exhibits a very small In/Ga phase width of x = 1.16 to 1.36 only, was obtained in the course of a systematic synthetic, crystallographic and bond theoretical investigation of mixed potassium trielides of the ternary system K-In-Ga. The compound, which was synthesized from nearly stoichiometric amounts of the elements at a maximum temperature of 500°C, crystallizes in a new orthorhombic crystal structure type [space group Cmmm, a = 1577.9(5), b = 3355.1(8), c = 655.2(2) pm, Z = 10, R 1 = 0.0471]. In the complex polyanion, the triels form two crystallographically different [Ga 12 ] icosahedra, which are present in a 1:2 ratio, and a previously unknown [M 13 ] "double-cluster" consisting of two vertex-sharing [M 7 ] pentagonal bipyramids. All clusters are connected among each other and via a four-bonded pure In and Ga

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Section: Electronic Structure Chemical Bonding and "Coloring" Aspectsmentioning

confidence: 99%

mentioning

confidence: 99%

The New Mixed Cluster Trielide K₃Ga_11–xIn_x (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

Falk

Meyer

Röhr

2017

Zeitschrift anorg allge chemie

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“…Moreover, the Au and Ge distribution in CaAu 2 Ge 2 35 appears to contradict the general postulates from Mulliken population analyses 56 or "coloring" analyses 5 of s-p bonded ThCr 2 Si 2 -type compounds. That is, those atoms with smaller electronegativities and larger sizes generally tend to occupy the so-called basal or planar sites (Wyckoff 4d), whereas the apical sites (4e) are favored for the stronger bonds and atoms of larger electronegativity (Mulliken electronegativities for Au and Ge are 5.77 and 4.6 eV 57 ).…”

Section: 34mentioning

confidence: 99%

Centric and Non-centric Ca₃Au_∼7.5Ge_∼3.5: Electron-Poor Derivatives of La₃Al₁₁. Syntheses, Structures, and Bonding Analyses

Lin¹,

Corbett²

2009

Inorg. Chem.

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Two La 3 Al 11 type derivatives have been discovered in the Ca-Au-Ge system and structurally characterized by single-crystal X-ray diffraction. Compositions Ca 3 Au 7.16(6) Ge 3.84(6) (1) and Ca 3 Au 7.43(9) Ge 3.57(9) (2) lie within a non-centric Imm2 phase region with a ≈ 4.40 A ˚, b ≈ 13.06 A ˚, c ≈ 9.60 A ˚. The Au-richer and electron-poorer Ca 3 Au 7.50(1) Ge 3.50(1) (3) and Ca 3 Au 8.01(1) Ge 2.99(1) (4) occur within a centric Pnnm phase region with a ≈ 9.50 A ˚, b ≈ 13.20 A ˚, c ≈ 4.43 A ˚. Both phases contain complex [Au,Ge] 11 6polyanionic networks made up of hexagonal and pentagonal prisms that are filled with the electropositive Ca atoms. Both 3:11 phases represent opposed 1 Â 3 Â 1 superstructure distortions of CaAu 2 Ge 2 (ThCr 2 Si 2 type, I4/mmm), the structure of which has also been re-determined in this work. Linear muffin-tin-orbital (LMTO) calculations reveal that the symmetry variations induced by changes of the Au contents in the present 3:11 phases are consequences of bonding and structural optimizations. The hypothetical "CaAu 2.33-2.67 Ge 1.33-1.00 0 0.33 " compositions, which are close to those of 1-4, follow through creation and elimination of vacancies within the electronegative networks of CaAu 2 Ge 2 .

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“…There are 70 ways to distribute two different kinds of atoms in 1:1 stoichiometry over the eight 6h and 2a Wyckoff sites in the primitive unit cell of the C14 structure type -or, in other words, to "color" the 2a and 6h sites with two colors [47][48][49]. Nine of these are of unique symmetry [50].…”

Section: High Coordination and Coloring A Laves Phasementioning

confidence: 99%

“…Under pressure, the constituents seem to resolve for themselves the question of what the optimal "coloring" of bcc lattice sites is, with equal contribution from three different "colors" [47][48][49]. Indeed, seeing the structures as colorings of the bcc lattice helps us to appreciate the complexity of structural choices available to this ternary.…”

Section: High Pressure Phases Of Libeb: Interpenetrating Cubic Sublatmentioning

confidence: 99%

LiBeB: A predicted phase with structural and electronic peculiarities

et al. 2012

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Beginning an in--depth analysis of binaries and ternaries in the Li/Be/B system, we examine the static structures and electronic properties of LiBeB (i.e 1:1:1) over a range of pressures. This as yet unknown compound is predicted to possess a stable ground state at 1 atm and some higher pressures. As the pressure rises, LiBeB goes through a diverse series of structures, beginning with metallic structures which feature chains and layers of atoms, progressing to structures built on "colorings" of the Laves phases, and containing helical arrangements of boron atoms, on to high pressure phases that are ternary variants of a bcc lattice. The density of states (DOS) at the Fermi level consistently falls in a pseudogap (sometimes a real gap is predicted); LiBeB is unlikely to be a good metal or superconductor. The distribution of the DOS follows what electronegativity would predict -Li electrons are 2 transferred to B. Some curious features of the LiBeB structures emerge, these include near--icosahedral coordination, independent of atom type; in a range of pressures a resemblance of the total DOS to that of metallic Be; and also a Dirac surface.3

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The “Coloring Problem” in Solids: How It Affects Structure, Composition and Properties

Cited by 228 publications

References 80 publications

The New Mixed Cluster Trielide K₃Ga_11–xIn_x (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

The New Mixed Cluster Trielide K₃Ga_11–xIn_x (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

Centric and Non-centric Ca₃Au_∼7.5Ge_∼3.5: Electron-Poor Derivatives of La₃Al₁₁. Syntheses, Structures, and Bonding Analyses

LiBeB: A predicted phase with structural and electronic peculiarities

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The “Coloring Problem” in Solids: How It Affects Structure, Composition and Properties

Cited by 228 publications

References 80 publications

The New Mixed Cluster Trielide K3Ga11–xInx (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

The New Mixed Cluster Trielide K3Ga11–xInx (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

Centric and Non-centric Ca3Au∼7.5Ge∼3.5: Electron-Poor Derivatives of La3Al11. Syntheses, Structures, and Bonding Analyses

LiBeB: A predicted phase with structural and electronic peculiarities

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The New Mixed Cluster Trielide K₃Ga_11–xIn_x (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

The New Mixed Cluster Trielide K₃Ga_11–xIn_x (x = 1.16–1.36): Synthesis, Crystal Chemistry, and Chemical Bonding

Centric and Non-centric Ca₃Au_∼7.5Ge_∼3.5: Electron-Poor Derivatives of La₃Al₁₁. Syntheses, Structures, and Bonding Analyses