TY - GEN A1 - Eckstein, Nadine A1 - Hohmann, Andrea A1 - Weihrich, Richard A1 - Nilges, Tom A1 - Schmidt, Peer T1 - Synthesis and Phase Relations of Single-Phase Fibrous Phosphorus T2 - Zeitschrift für anorganische und allgemeine Chemie N2 - Fibrous phosphorus is one of the known crystalline allotropes under standard pressure conditions. It has been predicted prior to its successful synthesis and structural characterization. The allotrope consists of parallel, tubular double strands of phosphorus, in contrast to the violet form of Hittorf's phosphorus, where the same strands are arranged in a perpendicular orientation towards each other. This structural similarity results in an almost identical energetic stability leading to a somehow problematic realization of single-phase materials. We herein report on the successful synthesis route to single phase fibrous phosphorus and the in situ characterization of its formation via the gas phase applying CuCl2 as a mineralizer. The sublimation pressure of fibrous phosphorus is slightly lower than the one of the black allotrope. This behavior indicates thermodynamic stability of fibrous phosphorus. KW - Allotropes;Phosphorus;High temperature gas balance Y1 - 2013 UR - http://onlinelibrary.wiley.com/doi/10.1002/zaac.201300327/abstract U6 - https://doi.org/10.1002/zaac.201300327 SN - 1521-3749 VL - Vol. 639 IS - 15 SP - 2741 EP - 2743 ER - TY - GEN A1 - Bawohl, Melanie A1 - Nilges, Tom A1 - Schmidt, Peer T1 - Temperature Initiated P-Polymerization in Solid [Cd3Cu]CuP10 T2 - Inorganic chemistry N2 - [Cd3Cu]CuP10 is the first representative of a class of compounds featuring polyphosphidic adamantine-analogous [P10] units, which tend to be fragmented and polymerized to [P6] rings and tubular [P26] units in the solid state. A new polyphosphide with nominal composition Cd15Cu10P46 results, featuring isolated and polymerized polyanions. Thermoanalytic experiments and phase analytic measurements substantiated the consecutive loss of P4 and Cd of the starting material via different intermediate steps. After P4 loss, the new polyphosphide occurred followed by various binary copper phosphides to the final product Cu3P. KW - Thermal Analysis, Solid State Synthesis, Crystal Structure, Polyphosphide Y1 - 2013 UR - http://pubs.acs.org/doi/abs/10.1021/ic401508n U6 - https://doi.org/10.1021/ic401508n SN - 1520-510X VL - 52 IS - 20 SP - 11895 EP - 11901 ER - TY - GEN A1 - Pielnhofer, Florian A1 - Schöneich, Michael A1 - Lorenz, Tobias A1 - Yan, Wenjie A1 - Nilges, Tom A1 - Weihrich, Richard A1 - Schmidt, Peer T1 - A rational approach to IrPTe – DFT and CalPhaD studies on phase stability, formation and structure of IrPT e T2 - Zeitschrift für anorganische und allgemeine Chemie N2 - Phase formation, stability, crystal and electronic structures of IrPTe are investigated from experiment and quantum chemical calculations. The phase formation is studied from thermodynamic data and CalPhaD modeling. Applying a high-temperature gas-balance a formation pathway for IrPTe is studied from the elements and the binary parent compounds IrTe2 and IrP2. The obtained paracostibite (CoSbS) type structure contains rarely occurring heteroatomic P-Te dumbbells. The stability of IrPTe and the found structure is studied from DFT calculations with respect to the elements, IrTe2 and IrP2, and possible polymorphs. Probable metastable modifications with XY dumbbells (as known for isoelectronic compounds like CoAsS) are obtained from systematic DFT modelling. Phase transitions are predicted form the equation of states (EOS). According to its electronic band structure IrPTe is predicted as small gap (Eg = 0.5 eV) semiconductor. KW - phase stability KW - DFT KW - gas balance KW - thermodynamic modelling KW - structure prediction Y1 - 2015 UR - http://onlinelibrary.wiley.com/doi/10.1002/zaac.201500149/abstract U6 - https://doi.org/10.1002/zaac.201500149 SN - 1521-3749 VL - 641 IS - 6 SP - 1099 EP - 1105 ER - TY - GEN A1 - Bachhuber, Frederik A1 - Appen, Jörg von A1 - Dronskowski, Richard A1 - Schmidt, Peer A1 - Nilges, Tom A1 - Pfitzner, Arno A1 - Weihrich, Richard T1 - Van der Waals interactions in selected allotropes of phosphorus T2 - Zeitschrift für Kristallografie N2 - Selected allotropes of phosphorus are investigated by different levels of density functional theory (DFT) calculations to evaluate the relative stability orders with a special focus on the role of van der Waals interactions.Phosphorus is an excellent reference system with a large number of allotropes. Starting from low-dimensional molecular (0D, white P) and polymer structures (1D, P nanorods) to layered (2D, black P) and tubular structures (2D and 3D, crystalline forms of red P), covalent structure motifs are interconnected by van der Waals interactions. They are a key factor for the correct energetic description of all P allotropes. A comparative study is carried out within the local density approximation (LDA) and the generalized gradient approximation (GGA), with and without implementation of a dispersion correction by Grimme (GGA-D2). Our intention is to achieve a reasonable agreement of our calculations with experimental data, the plausibility of energy values, and the treatment of long-range interactions. The effect of van der Waals interactions is exemplified for the interlayer distances of black phosphorous and its electronic structure. KW - allotropes KW - band structure KW - DFT KW - phosphorous KW - stability KW - van der Waals Y1 - 2015 U6 - https://doi.org/10.1515/zkri-2014-1800 SN - 2196-7105 VL - 230 IS - 2 SP - 107 EP - 115 ER - TY - GEN A1 - Bachhuber, Frederik A1 - Appen, Jörg von A1 - Dronskowski, Richard A1 - Schmidt, Peer A1 - Nilges, Tom A1 - Pfitzner, Arno A1 - Weihrich, Richard T1 - The Extended Stability Range of Phosphorus Allotropes T2 - Angewandte Chemie / International edition N2 - Phosphorus displays fascinating structural diversity and the discovery of new modifications continues to attract attention. In this work, a complete stability range of known and novel crystalline allotropes of phosphorus is described for the first time. This includes recently discovered tubular modifications and the prediction of not-yet-known crystal structures of [P12] nanorods and not-yet-isolated [P14] nanorods. Despite significant structural differences, all P allotropes consist of covalent substructures, which are held together by van der Waals interactions. Their correct reproduction by ab initio calculations is a core issue of current research. While some predictions with the established DFT functionals GGA and LDA differ significantly from experimental data in the description of the P allotropes, consistently excellent agreement with the GGA-D2 approach is used to predict the solid structures of the P nanorods. KW - density functional calculations KW - phosphorus KW - structure elucidation KW - van der Waals interactions Y1 - 2014 UR - http://onlinelibrary.wiley.com/doi/10.1002/anie.201404147/full U6 - https://doi.org/10.1002/anie.201404147 SN - 1521-3773 VL - 53 IS - 43 SP - 11629 EP - 11633 ER - TY - GEN A1 - Osters, Oliver A1 - Nilges, Tom A1 - Schöneich, Michael A1 - Schmidt, Peer A1 - Rothballer, Jan A1 - Pielnhofer, Florian A1 - Weihrich, Richard T1 - Cd4Cu7As, the first representative of a fully ordered, orthorhombically distorted MgCu2 Laves phase T2 - Inorganic Chemistry N2 - The ternary Laves phase Cd4Cu7As is the first intermetallic compound in the system Cu–Cd–As and a representative of a new substitution variant for Laves phases. It crystallizes orthorhombically in the space group Pnnm (No. 58) with lattice parameters a = 9.8833(7) Å; b = 7.1251(3) Å; c = 5.0895(4) Å. All sites are fully occupied within the standard deviations. The structure can be described as typical Laves phase, where Cu and As are forming vertex-linked tetrahedra and Cd adopts the structure motive of a distorted diamond network. Cd4Cu7As was prepared from stoichiometric mixtures of the elements in a solid state reaction at 1000 °C. Magnetic measurements are showing a Pauli paramagnetic behavior. During our systematical investigations within the ternary phase triangle Cd–Cu–As the cubic C15-type Laves phase Cd4Cu6.9(1)As1.1(1) was structurally characterized. It crystallizes cubic in the space group Fd3m̅ with lattice parameter a = 7.0779(8) Å. Typically for quasi-binary Laves phases Cu and As are both occupying the 16c site. Chemical bonding, charge transfer and atomic properties of Cd4Cu7As were analyzed by band structure, ELF, and AIM calculations. On the basis of the general formula for Laves phases AB2, Cd is slightly positively charged forming the A substructure, whereas Cu and As represent the negatively charged B substructure in both cases. The crystal structure distortion is thus related to local effects caused by Arsenic that exhibits a larger atomic volume (18 Å3 compared to 13 Å3 for Cu) and higher ionicity in bonding. Y1 - 2012 UR - http://pubs.acs.org/doi/abs/10.1021/ic3005213 U6 - https://doi.org/10.1021/ic3005213 SN - 1520-510X VL - 51 SP - 8119 EP - 8127 ER - TY - GEN A1 - Schmidt, Peer A1 - Schöneich, Michael A1 - Bawohl, Melanie A1 - Nilges, Tom A1 - Weihrich, Richard T1 - Thermal analysis detecting equilibrium conditions: The use of the high temperature gas balance for thermogravimetric measurements T2 - Journal of Thermal Analysis and Calorimetry N2 - Several methods are established in thermal analysis to investigate phase formation, phase transition, and decomposition reactions. The analysis of phase equilibria with volatile components is particularly feasible by using standard method of thermogravimetry. Hardly any investigations of phase formation reactions are possible to realize if one of the components is lost by vaporization. By using the “High-Temperature Gas-Balance” (HTGB), the vapor phase is enclosed in a silica ampoule and thus forms an equilibrium gas phase in permanent contact with the solid phase. The measurement signal Δmmeas is caused by change of the leverage of the horizontal balance support during evaporation and condensation. The application of the HTGB allows the analysis of solid–gas equilibria in the working range from 0.01 till 15 bar at temperatures up to 1,100 °C. The first comparison of evaporation reactions determined by standard thermogravimetric analyses and by measurements using the HTGB is given for the inorganic systems: P, As, SeO2, PtI2, and Hg/I. KW - High-Temperature Gas-Balance KW - Thermogravimetry KW - Vapor pressure KW - Equilibrium measurements Y1 - 2012 UR - http://www.akademiai.com/doi/pdf/10.1007/s10973-011-2107-3 U6 - https://doi.org/10.1007/s10973-011-2107-3 SN - 1572-8943 VL - 110 IS - 3 SP - 1511 EP - 1521 ER - TY - GEN A1 - Osters, Oliver A1 - Nilges, Tom A1 - Bachhuber, Frederik A1 - Pielnhofer, Florian A1 - Weihrich, Richard A1 - Schöneich, Michael A1 - Schmidt, Peer T1 - Synthesis and Identification of Metastable Compounds: Black Arsenic—Science or Fiction? T2 - Angewandte Chemie / International edition N2 - Back in black: All metastable and stable phases can be identified for the solid solution arsenic/phosphorus by a combination of quantum-chemical calculations and investigations of the phase formation. Reaction paths for phase formations and transitions in situ were also evaluated. The results show that orthorhombic black arsenic (o-As) is metastable in pure form and has only been previously obtained by stabilizing impurities. KW - arsenic KW - metastable phases KW - phase formation KW - phosphorus KW - solid-state structures Y1 - 2012 UR - http://onlinelibrary.wiley.com/doi/10.1002/anie.201106479/abstract U6 - https://doi.org/10.1002/anie.201106479 SN - 1521-3773 VL - 51 IS - 12 SP - 2994 EP - 2997 ER - TY - GEN A1 - Pfister, Daniela A1 - Schäfer, Konrad A1 - Ott, Claudia A1 - Gerke, Birgit A1 - Pöttgen, Rainer A1 - Janka, Oliver A1 - Baumgartner, Maximilian A1 - Efimova, Anastasia A1 - Hohmann, Andrea A1 - Schmidt, Peer A1 - Venkatachalam, Sabarinathan A1 - Wüllen, Leo van A1 - Schürmann, Ulrich A1 - Kienle, Lorenz A1 - Duppel, Viola A1 - Parzinger, Eric A1 - Miller, Bastian A1 - Becker, Jonathan A1 - Holleitner, Alexander A1 - Weihrich, Richard A1 - Nilges, Tom T1 - Inorganic double helices in semiconducting SnIP T2 - Advanced Materials N2 - SnIP is the first atomic-scale double helical semiconductor featuring a 1.86 eV bandgap, high structural and mechanical flexibility, and reasonable thermal stability up to 600 K. It is accessible on a gram scale and consists of a racemic mixture of right- and left-handed double helices composed by [SnI] and [P] helices. SnIP nanorods <20 nm in diameter can be accessed mechanically and chemically within minutes. KW - Helical semiconductor Y1 - 2016 UR - http://onlinelibrary.wiley.com/doi/10.1002/adma.201603135/full U6 - https://doi.org/10.1002/adma.201603135 SN - 1521-4095 VL - 28 IS - 44 SP - 9783 EP - 9791 ER - TY - GEN A1 - Schöneich, Michael A1 - Hohmann, Andrea A1 - Schmidt, Peer A1 - Pielnhofer, Florian A1 - Bachhuber, Frederik A1 - Weihrich, Richard A1 - Osters, Oliver A1 - Köpf, Marianne A1 - Nilges, Tom T1 - Element allotropes and polyanion compounds of pnicogenes and chalcogenes: stability, mechanisms of formation, controlled synthesis and characterization T2 - Zeitschrift für Kristallographie - Crystalline Materials N2 - The application of the EnPhaSyn (theoretical Energy diagrams, experimental Phase formation, Synthesis and characterisation) concept is reviewed with respect to prediction of structures and stability of element allotropes and compound polymorphs, their phase formation and transition processes, and their directed synthesis, respectively. Therein, the relative energetical stability (En) of target compounds and possible decomposition are determined from quantum chemical DFT calculations. Phase formation and transition (Pha) is probed by a gas balance method, developed as high temperature gas balance concept. It helped to study the synthesis and stability range of several compounds experimentally. Applications of the concept and synthesis principles (Syn) of non-equilibrium phases are presented for allotropes of P, As, P1-xAsx, as well as binary and ternary compounds including the Zintl and Laves like phases IrPTe, NiP2, CoSbS, NiBiSe, Li0.2CdP2, Cu3CdCuP10, and Cd4Cu7As. KW - Arsenic KW - Phosporus KW - DFT KW - energy diagram KW - polymorph structure Y1 - 2017 UR - https://www.degruyter.com/view/j/zkri.ahead-of-print/zkri-2016-1966/zkri-2016-1966.xml U6 - https://doi.org/10.1515/zkri-2016-1966 SN - 2194-4946 VL - 232 IS - 1-3 SP - 91 EP - 105 ER - TY - GEN A1 - Schmidt, Peer A1 - Hohmann, Andrea A1 - Nilges, Tom A1 - Köpf, Marianne A1 - Weihrich, Richard T1 - Synthesis of Element Allotropes of Arsenic and Phosphorus by Application of Electromotive Series of Solids T2 - Zeitschrift für Anorganische und Allgemeine Chemie N2 - Calculation of electromotive series of solids allows easy prediction of reaction pathways[1]. Using the electromotive series of systems As-P-O and As-P-X (X = F, Cl, Br, I) the formation of element allotropes via the oxide and halide compounds in thermite type reactions can be deduced: phosphorous will reduce the arsenic oxides to elemental arsenic, forming grey or black allotrope, depending on reaction mixture composition. KW - Element allotropes KW - Arsenic KW - Phosphorus Y1 - 2014 UR - http://onlinelibrary.wiley.com/doi/10.1002/zaac.201490026/full U6 - https://doi.org/10.1002/zaac.201490026 SN - 1521-3749 VL - 640 IS - 11 SP - 2386 ER - TY - GEN A1 - Schöneich, Michael A1 - Lorenz, Tobias A1 - Bawohl, Melanie A1 - Nilges, Tom A1 - Schmidt, Peer T1 - Phase Formation in the System Hg/P/I Induced by Evaporation Pressure T2 - Zeitschrift für Anorganische und Allgemeine Chemie KW - High-temperature Gas-balance Y1 - 2010 UR - http://onlinelibrary.wiley.com/doi/10.1002/zaac.201009042/full U6 - https://doi.org/10.1002/zaac.201009042 N1 - Poster VL - 636 IS - 11 SP - S. 2070 ER - TY - GEN A1 - Schmidt, Peer A1 - Schöneich, Michael A1 - Nilges, Tom A1 - Weihrich, Richard T1 - Identification of Metastable States in Heterogeneous Phase Formation T2 - Zeitschrift für Anorganische und Allgemeine Chemie KW - Phosphorus KW - High-temperature Gas-balance Y1 - 2012 UR - http://onlinelibrary.wiley.com/doi/10.1002/zaac.201204134/full U6 - https://doi.org/10.1002/zaac.201204134 N1 - Poster VL - 638 IS - 10 SP - S. 1633 ER - TY - CHAP A1 - Nilges, Tom A1 - Schmidt, Peer A1 - Weihrich, Richard ED - Scott, Robert A. T1 - Phosphorus: The Allotropes, Stability, Synthesis, and Selected Applications T2 - Encyclopedia of Inorganic and Bioinorganic Chemistry N2 - Phosphorus, first found in the seventeenth century, played an important role in the definition of the element term by Lavoisier and thus shaped the beginning of the era of modern chemistry. It was discovered for the first time in the most unstable crystalline modification—the white phosphorus. Today, a variety of experimentally proven allotropes are known. The most common allotropes, such as black, violet, and fibrous phosphorus, are described here with respect to their synthesis, crystal structures, thermal, and thermodynamic properties. Besides, more than 50 crystalline allotropes have been predicted, and their stabilities have been estimated using quantum‐chemical methods. This way, phosphorus becomes one of the most structurally variable elements of the periodic table. In this article, some of the most reasonable and sophisticated calculations are presented. The applications of elemental phosphorus are mainly connected with its semiconducting properties. Thus, the development of current applications is strongly related to new synthesis methods for direct preparation of individual, phase pure allotropic forms of phosphorus. The past decade supplied basic results on the formation of black phosphorus and other modifications, primarily using the mineralizer concept. Related to graphene and other two‐dimensional, layered structures, phosphorene is of drastically rising interest. The pertinent modifications are characterized by corrugated arrangement of six‐membered P‐rings, where both the boat conformation and the chair conformation are known. The application of phosphorene is in a jumping evolution. Currently, phosphorene is already in use in manifold ways, including as a sensor, optical device, transistor, energy‐conversion material, and supercapacitor material. KW - Crystal growth KW - Chemical vapor transport KW - Crystal structure KW - Phosphorus KW - High-temperature Gas-balance KW - Thermal analysis KW - DFT Y1 - 2018 UR - https://onlinelibrary.wiley.com/doi/pdf/10.1002/9781119951438.eibc2643 SN - 978-1-119-95143-8 U6 - https://doi.org/10.1002/9781119951438.eibc2643 SP - 1 EP - 19 PB - John Wiley Sons CY - Hoboken, US ET - 2. Auflage ER - TY - GEN A1 - Pielnhofer, Florian A1 - Bachhuber, Frederik A1 - Schmidt, Peer A1 - Nilges, Tom A1 - Weihrich, Richard T1 - Mit DFT-Modellierungen zu neuen Polyanionenverbindungen T2 - Zeitschrift für Anorganische und Allgemeine Chemie N2 - Verbindungen mit ionischen Baueinheiten erweisen sich als geeignete Materialien zur Energie- und Ressourcennutzung. Beispiele sind Li-Elektrodenmaterialien oder neue Thermoelektrika, die aufgrund ihrer Teilstrukturen schaltbar werden. Das Design neuer funktionaler Materialien verlangt dabei nach einem grundlegenden Verständnis von Struktur-Eigenschafts-Beziehungen, metastabilen Strukturen und Umwandlungen. Dies bedarf des Einsatzes kombinierter experimenteller und theoretischer Methoden. Zur systematischen Erforschung metastabiler Strukturen wurde jüngst das Konzept der Strukturvorhersage in Energielandschaften mit ab initio Methoden auf das System P1-xAsx angewandt und mit experimentellen Messungen verknüpft. Im nächsten Schritt wurden Verbindungen mit ionischen Teilstrukturen des As, Sb, Se und Te untersucht. Modellhaft wurden nun Zintl-Systemen wie IrPTe und PtSnTe neue mögliche metastabile Strukturen identifiziert und auf Funktionalisierungen untersucht. KW - DFT KW - Chalcogenides Y1 - 2012 UR - http://onlinelibrary.wiley.com/doi/10.1002/zaac.201204137/full U6 - https://doi.org/10.1002/zaac.201204137 N1 - Poster VL - 638 IS - 10 SP - S. 1634 ER - TY - GEN A1 - Nilges, Tom A1 - Osters, Oliver A1 - Schmidt, Peer A1 - Schöneich, Michael A1 - Weihrich, Richard A1 - Bachhuber, Frederik T1 - Untersuchungen zur Bildung von schwarzem Arsen T2 - Zeitschrift für Anorganische und Allgemeine Chemie N2 - Das Mineralisatorkonzept für Polypniktide, basierend auf PbI2 als Mineralisator, wurde erfolgreich zur Synthese der festen Lösung von ortho-rhombischem, schwarzen As1–xPx eingesetzt (x = 0.17-1). Die Zellparameter von As0.83P0.17 sind identisch mit den Literaturwerten des As(schwarz). Aus Pulver- und Einkristalldaten bei variabler Zusammensetzung ist es möglich, das Zellvolumen und die Gitterparameter von reinem, schwarzen Arsen abzuleiten. Die Analyse der Phasenbildung basiert auf der Bestimmung der Gleichgewichtsdrücke der Intermediate Au2P3 und Asgrau sowie von PbI2 im Vergleich zu As1–xPx(schwarz): Die Kondensation erfolgt unterhalb 600 °C aus einer komplexen Gasphase (u.a. AsnP4–n). KW - Phosphorus KW - Arsenic KW - Crystal structure Y1 - 2010 UR - http://onlinelibrary.wiley.com/doi/10.1002/zaac.201008019/full U6 - https://doi.org/10.1002/zaac.201008019 VL - 636 IS - 11 SP - S. 46 ER - TY - BOOK A1 - Schmidt, Peer A1 - Nilges, Tom T1 - Allgemeine Chemie, Teil 5: Wissenschaftliches Arbeiten N2 - Prinzipien des wissenschaftlichen Arbeitens und Methodik zur Erstellung von Protokollen, Kurzberichten, Projektberichten und wissenschaftlichen Publikationen KW - Allgemeine Chemie KW - wissenschaftliches Arbeiten KW - wissenschaftliche Berichte und Publikationen Y1 - 2015 SN - 978-3-662-47539-3 PB - Springer Spektrum CY - Berlin [u.a.] ER -