Bonding Schemes for Compounds with the Pyrite, Marcasite, and Arsenopyrite Type Structures.

Brostigen, Gunnar; Kjekshus, Arne; Liaaen‐Jensen, S.; Rasmussen, S. E.; Shimizu, Akira

doi:10.3891/acta.chem.scand.24-2993

Cited by 108 publications

(51 citation statements)

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“…A detailed discussion on the relationships between the pyrite, marcasite, and arsenopyrite type can be found in contributions by A. Kjekshus. [62][63][64] Many depictions of the unit cells found in the literature contain a rather unclear connection of coordination polyhedra or appear as mere congeries of the atoms of the unit cell. Here, we want to introduce a straightforward graphical representation with emphasis on common structural fragments to allow for a comparison of the present structure types.…”

Section: Crystal Structuresmentioning

confidence: 99%

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

Bachhuber

Rothballer

Sohnel

et al. 2013

The Journal of Chemical Physics

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In the course of the recent advances in chemical structure prediction, a straightforward type of diagram to evaluate phase stabilities is presented based on an expedient example. Crystal structures and energetic stabilities of dipnictides NiPn2 (Pn = N, P, As, Sb, Bi) are systematically investigated by first principles calculations within the framework of density functional theory using the generalized gradient approximation to treat exchange and correlation. These dipnictides show remarkable polymorphism that is not yet understood systematically and offers room for the discovery of new phases. Relationships between the concerned structures including the marcasite, the pyrite, the arsenopyrite/CoSb2, and the NiAs2 types are highlighted by means of common structural fragments. Electronic stabilities of experimentally known and related AB2 structure types are presented graphically in so-called stability diagrams. Additionally, competing binary phases are taken into consideration in the diagrams to evaluate the stabilities of the title compounds with respect to decomposition. The main purpose of the stability diagrams is the introduction of an image that enables the estimation of phase stabilities at a single glance. Beyond that, some of the energetically favored structure types can be identified as potential new phases.

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Section: Crystal Structuresmentioning

confidence: 99%

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

Bachhuber

Rothballer

Sohnel

et al. 2013

The Journal of Chemical Physics

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“…A detailed review of these models will not be given here and the reader is referred to the original papers (Hulliger & Mooser, 1965;Pearson, 1965;Brostigen & Kjekshus, 1970;Goodenough, 1972). It is, however, remarkable that not one of the more recent bonding models allows for metal-metal bonding in the loellingites, quite in contrast with the generally accepted view that short interatomic distances indicate bonding, especially when alternate structures are competing (as is the pyrite structure in this case), where the short nonbonding interactions could be avoided.…”

Section: Marcasites and Arsenopyritesmentioning

confidence: 99%

“…* Table I of the paper by Brostigen & Kjekshus (1970) lists a d ° defect marcasite Mo,~3As2 with short c axis. This compound seems to contradict our bonding proposal [but might be considered as supporting Goodenough's (1972) model] since a long c axis would be expected for a d ° compound where no T-T bonds are possible.…”

Section: Marcasites and Arsenopyritesmentioning

confidence: 99%

High-pressure MnP₄, a polyphosphide with Mn–Mn pairs

Jeitschko¹,

Donohue²

1975

Acta Crystallogr Sect B

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The new compound MnP4 was prepared by reaction of the elemental components at pressures of 30-55 kbar in a tetrahedral anvil high-pressure device. It is a diamagnetic semiconductor with an activation energy of 0-14 eV and crystallizes with space group C2/c, a= 10.513 (1), b= 5.0944 (4), c= 21-804 (2) A, fl=94-71 (1) °, and Z= 16. The structure was determined from single-crystal counter data by Patterson and Fourier methods and refined to a conventional R of 0.051 for 1765 reflections. The Mn atoms are in octahedral P coordination, and the P atoms are tetrahedrally coordinated by Mn and P atoms. The Mn atoms have formal oxidation number 2 + (d 5 configuration). Four MnP6 octahedra share edges to form a linear array of four Mn atoms. The Mn atoms are displaced from the centers of the octahedra toward one another to form pairs with a resulting Mn-Mn bonding distance of 2.941 A, thus accounting for the diamagnetism. Average Mn-P and P-P distances are 2.282 and 2-225 ,£,, respectively. MnP4 can be described as an eight-layer stacking variant of the two-layer CrP4 structure, although bonding within and between the layers is of equal strength. Qualitative MO bonding models for the MnP4 and CrP4 structures are presented that allow rationalization of magnetic and conductive properties. A similar bonding proposal is made for the marcasite and arsenopyrite structures which, as is the case for CrP4 and MnP4, have TPo octahedra linked via edges, with transition metal atoms forming infinite strings and pairs, respectively.

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“…This value is longer than that of the low-pressure form and nearly equal to sum of the metallic radii. According to the literature [1], the average Cr-Sb distance in the low-pressure marcasite-type, in which the bond nature is believed to be mixed ionic and covalent character, is 2.708 A. The bonding scheme in the marcasite -type phase is explained as C r4'(Sb)`.…”

Section: Resultsmentioning

confidence: 99%

“…The common features of these closely related compounds are the formation of X-X dimer (dumb-bells) and the mixed ionic and covalent character of the chemical bonds [1,2]. The X-X bond distances in these compounds are nearly equal to sum of the single bond tetrahedral covalent radii.…”

Section: Introductionmentioning

confidence: 99%

High Pressure Phase Transition of CrSb2.

Takizawa

Uhcda

Shimada

1998

THE REVIEW OF HIGH PRESSURE SCIENCE AND TECHNOLOGY

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Anewhigh-pressure phase of CrSb2 has been synthesized from the marcasite-type ambient pressure phase by high-pressure/ temperature treatment above 5.5 GPa. The crystal structure of the high-pressure phase is body-centered tetragonal, which is assigned as CuAIZ type structure. The bond nature in the high-pressure phase is metallic, in contrast to the mixed ionic and covalent character in the marcasite-type phase. The phase transition, marcasite-type to CuAIZ type, accompanies 11% volume decrease and a change of d-electron character from localized to itinerant.[high-pressure synthesis, phase transition, marcasite-type, CuA12-type, pnictides]

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Bonding Schemes for Compounds with the Pyrite, Marcasite, and Arsenopyrite Type Structures.

Cited by 108 publications

References 0 publications

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

High-pressure MnP₄, a polyphosphide with Mn–Mn pairs

High Pressure Phase Transition of CrSb2.

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Bonding Schemes for Compounds with the Pyrite, Marcasite, and Arsenopyrite Type Structures.

Cited by 108 publications

References 0 publications

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

High-pressure MnP4, a polyphosphide with Mn–Mn pairs

High Pressure Phase Transition of CrSb2.

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Product

Resources

About

High-pressure MnP₄, a polyphosphide with Mn–Mn pairs