Special Issue "First-Principles Prediction of Structures and Properties in Crystals"

A special issue of Crystals (ISSN 2073-4352). This special issue belongs to the section "Crystalline Materials".

Deadline for manuscript submissions: closed (30 June 2019).

Special Issue Editors

Guest Editor
Dr. Andreas Hermann Website E-Mail
Centre for Science at Extreme Conditions, School of Physics and Astronomy and SUPA, The University of Edinburgh, EH9 3FD Edinburgh, UK
Interests: condensed matter physics; chemical physics; density functional theory; crystal structure prediction; extreme conditions science
Guest Editor
Dr. Dominik Kurzydlowski Website E-Mail
Faculty of Mathematics and Natural Sciences, Cardinal Stefan Wyszynski University, Warsaw, Poland

Special Issue Information

Dear Colleagues,

The prediction of the crystal structures and properties of compounds purely from electronic structure calculations, without input from experimental data, has become a large research area spanning physics, chemistry, geosciences, and materials science. Its success relies on electronic structure methods (most often density functional theory) that can accurately map the crystalline configurational space of a given compound, together with the development of efficient survey algorithms of said space, for instance through evolutionary or genetic algorithms, particle swarm optimisation techniques, high-throughput screening, and others. In addition to finding energetically most stable structures, recent software developments also allow targeted searches for desirable properties, such as specific electronic band gaps or mechanical hardness.

Crystal structure prediction has seen its biggest successes in areas where the chemical space is too large to explore exhaustively through synthesis; where experiments are limited and difficult (e.g., under extreme conditions); and, generally, where chemical intuition and other approaches to rationalise structural choices fail. It therefore complements experiments not only in an explanatory but a truly explorative manner.

This Special Issue aims at taking stock of the current state of the field, highlighting the capabilities (and perhaps, current shortcomings or future opportunities) of first-principles prediction methods of crystal structures and properties. Scientists across a range of disciplines are invited to contribute to this collection. The topics presented in the keywords cover broadly the scope of this Special Issue, but do not restrict it; innovative contributions are particularly welcome.

Dr. Andreas Hermann
Dr. Dominik Kurzydlowski
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Crystals is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1400 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • crystal structure prediction techniques
  • high-throughput screening
  • constraint sampling
  • fitness functions
  • materials properties
  • low-dimensional materials and interfaces
  • new chemistry
  • extreme conditions

Published Papers (8 papers)

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Editorial

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Open AccessEditorial
First-Principles Prediction of Structures and Properties in Crystals
Crystals 2019, 9(9), 463; https://doi.org/10.3390/cryst9090463 - 04 Sep 2019
Abstract
The term “first-principles calculations” is a synonym for the numerical determination of the electronic structure of atoms, molecules, clusters, or materials from ‘first principles’, i [...] Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)

Research

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Open AccessArticle
A First-Principles Exploration of NaxSy Binary Phases at 1 atm and Under Pressure
Crystals 2019, 9(9), 441; https://doi.org/10.3390/cryst9090441 - 24 Aug 2019
Cited by 1
Abstract
Interest in Na-S compounds stems from their use in battery materials at 1 atm, as well as the potential for superconductivity under pressure. Evolutionary structure searches coupled with Density Functional Theory calculations were employed to predict stable and low-lying metastable phases of sodium [...] Read more.
Interest in Na-S compounds stems from their use in battery materials at 1 atm, as well as the potential for superconductivity under pressure. Evolutionary structure searches coupled with Density Functional Theory calculations were employed to predict stable and low-lying metastable phases of sodium poor and sodium rich sulfides at 1 atm and within 100–200 GPa. At ambient pressures, four new stable or metastable phases with unbranched sulfur motifs were predicted: Na2S3 with C 2 / c and Imm2 symmetry, C 2 -Na2S5 and C 2 -Na2S8. Van der Waals interactions were shown to affect the energy ordering of various polymorphs. At high pressure, several novel phases that contained a wide variety of zero-, one-, and two-dimensional sulfur motifs were predicted, and their electronic structures and bonding were analyzed. At 200 GPa, P 4 / m m m -Na2S8 was predicted to become superconducting below 15.5 K, which is close to results previously obtained for the β -Po phase of elemental sulfur. The structures of the most stable M3S and M4S, M = Na, phases differed from those previously reported for compounds with M = H, Li, K. Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)
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Open AccessArticle
Simultaneous Prediction of the Magnetic and Crystal Structure of Materials Using a Genetic Algorithm
Crystals 2019, 9(9), 439; https://doi.org/10.3390/cryst9090439 - 23 Aug 2019
Cited by 1
Abstract
We introduce a number of extensions and enhancements to a genetic algorithm for crystal structure prediction, to make it suitable to study magnetic systems. The coupling between magnetic properties and crystal structure means that it is essential to take a holistic approach, and [...] Read more.
We introduce a number of extensions and enhancements to a genetic algorithm for crystal structure prediction, to make it suitable to study magnetic systems. The coupling between magnetic properties and crystal structure means that it is essential to take a holistic approach, and we present for the first time, a genetic algorithm that performs a simultaneous global optimisation of both magnetic structure and crystal structure. We first illustrate the power of this approach on a novel test system—the magnetic Lennard–Jones potential—which we define. Then we study the complex interface structures found at the junction of a Heusler alloy and a semiconductor substrate as found in a proposed spintronic device and show the impact of the magnetic interface structure on the device performance. Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)
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Open AccessArticle
Quest for Compounds at the Verge of Charge Transfer Instabilities: The Case of Silver(II) Chloride
Crystals 2019, 9(8), 423; https://doi.org/10.3390/cryst9080423 - 15 Aug 2019
Cited by 1
Abstract
Electron-transfer processes constitute one important limiting factor governing stability of solids. One classical case is that of CuI2, which has never been prepared at ambient pressure conditions due to feasibility of charge transfer between metal and nonmetal (CuI2 → CuI [...] Read more.
Electron-transfer processes constitute one important limiting factor governing stability of solids. One classical case is that of CuI2, which has never been prepared at ambient pressure conditions due to feasibility of charge transfer between metal and nonmetal (CuI2 → CuI + ½ I2). Sometimes, redox instabilities involve two metal centers, e.g., AgO is not an oxide of divalent silver but rather silver(I) dioxoargentate(III), Ag(I)[Ag(III)O2]. Here, we look at the particularly interesting case of a hypothetical AgCl2 where both types of redox instabilities operate simultaneously. Since standard redox potential of the Ag(II)/Ag(I) redox pair reaches some 2 V versus Normal Hydrogen Electrode (NHE), it might be expected that Ag(II) would oxidize Cl anion with great ease (standard redox potential of the ½ Cl2/Cl pair is + 1.36 V versus Normal Hydrogen Electrode). However, ionic Ag(II)Cl2 benefits from long-distance electrostatic stabilization to a much larger degree than Ag(I)Cl + ½ Cl2, which affects relative stability. Moreover, Ag(II) may disproportionate in its chloride, just like it does in an oxide; this is what AuCl2 does, its formula corresponding in fact to Au(I)[Au(III)Cl4]. Formation of polychloride substructure, as for organic derivatives of Cl3 anion, is yet another possibility. All that creates a very complicated potential energy surface with a few chemically distinct minima i.e., diverse polymorphic forms present. Here, results of our theoretical study for AgCl2 will be presented including outcome of evolutionary algorithm structure prediction method, and the chemical identity of the most stable form will be uncovered together with its presumed magnetic properties. Contrary to previous rough estimates suggesting substantial instability of AgCl2, we find that AgCl2 is only slightly metastable (by 52 meV per formula unit) with respect to the known AgCl and ½ Cl2, stable with respect to elements, and simultaneously dynamically (i.e., phonon) stable. Thus, our results point out to conceivable existence of AgCl2 which should be targeted via non-equilibrium approaches. Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)
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Open AccessArticle
Insight into the Optoelectronic and Thermoelectric Properties of Mn Doped ZnTe from First Principles Calculation
Crystals 2019, 9(5), 247; https://doi.org/10.3390/cryst9050247 - 13 May 2019
Cited by 1
Abstract
Using DFT band structure simulations together with semi-classical Boltzmann transport kinetics equations, we have explored the optoelectronic and transport features of MnxZn1−xTe (x = 8% and 16%) crystals. Optimization of the doping and related technological processes it is extremely [...] Read more.
Using DFT band structure simulations together with semi-classical Boltzmann transport kinetics equations, we have explored the optoelectronic and transport features of MnxZn1−xTe (x = 8% and 16%) crystals. Optimization of the doping and related technological processes it is extremely important for optimization of the technological parameters. The Generalized Gradient Approximation is applied to compute the corresponding band structure parameters. We have applied the Generalized Gradient Approximation Plus U (GGA+U). We have demonstrated that MnxZn1−xTe (x = 8% and 16%) is a direct type band semiconductor with principal energy gap values equal to 2.20 and 2.0 eV for x = 8% and 16%, respectively. The energy gap demonstrates significant decrease with increasing Mn content. Additionally, the origin of the corresponding bands is explored from the electronic density of states. The optical dispersion functions are calculated from the spectra of dielectric function. The theoretical simulations performed unambiguously showed that the titled materials are simultaneously promising optoelectronic and thermoelectric devices. The theoretical simulations performed showed ways for amendment of their transport properties by replacement of particular ions. Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)
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Open AccessArticle
Van der Waals Density Functional Theory vdW-DFq for Semihard Materials
Crystals 2019, 9(5), 243; https://doi.org/10.3390/cryst9050243 - 08 May 2019
Cited by 2
Abstract
There are a large number of materials with mild stiffness, which are not as soft as tissues and not as strong as metals. These semihard materials include energetic materials, molecular crystals, layered materials, and van der Waals crystals. The integrity and mechanical stability [...] Read more.
There are a large number of materials with mild stiffness, which are not as soft as tissues and not as strong as metals. These semihard materials include energetic materials, molecular crystals, layered materials, and van der Waals crystals. The integrity and mechanical stability are mainly determined by the interactions between instantaneously induced dipoles, the so called London dispersion force or van der Waals force. It is challenging to accurately model the structural and mechanical properties of these semihard materials in the frame of density functional theory where the non-local correlation functionals are not well known. Here, we propose a van der Waals density functional named vdW-DFq to accurately model the density and geometry of semihard materials. Using β -cyclotetramethylene tetranitramine as a prototype, we adjust the enhancement factor of the exchange energy functional with generalized gradient approximations. We find this method to be simple and robust over a wide tuning range when calibrating the functional on-demand with experimental data. With a calibrated value q = 1.05 , the proposed vdW-DFq method shows good performance in predicting the geometries of 11 common energetic material molecular crystals and three typical layered van der Waals crystals. This success could be attributed to the similar electronic charge density gradients, suggesting a wide use in modeling semihard materials. This method could be useful in developing non-empirical density functional theories for semihard and soft materials. Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)
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Open AccessArticle
Insight into Physical and Thermodynamic Properties of X3Ir (X = Ti, V, Cr, Nb and Mo) Compounds Influenced by Refractory Elements: A First-Principles Calculation
Crystals 2019, 9(2), 104; https://doi.org/10.3390/cryst9020104 - 18 Feb 2019
Cited by 1
Abstract
The effects of refractory metals on physical and thermodynamic properties of X3Ir (X = Ti, V, Cr, Nb and Mo) compounds were investigated using local density approximation (LDA) and generalized gradient approximation (GGA) methods within the first-principles calculations based on density [...] Read more.
The effects of refractory metals on physical and thermodynamic properties of X3Ir (X = Ti, V, Cr, Nb and Mo) compounds were investigated using local density approximation (LDA) and generalized gradient approximation (GGA) methods within the first-principles calculations based on density functional theory. The optimized lattice parameters were both in good compliance with the experimental parameters. The GGA method could achieve an improved structural optimization compared to the LDA method, and thus was utilized to predict the elastic, thermodynamic and electronic properties of X3Ir (X = Ti, V, Cr, Nb and Mo) compounds. The calculated mechanical properties (i.e., elastic constants, elastic moduli and elastic anisotropic behaviors) were rationalized and discussed in these intermetallics. For instance, the derived bulk moduli exhibited the sequence of Ti3Ir < Nb3Ir < V3Ir < Cr3Ir < Mo3Ir. This behavior was discussed in terms of the volume of unit cell and electron density. Furthermore, Debye temperatures were derived and were found to show good consistency with the experimental values, indicating the precision of our calculations. Finally, the electronic structures were analyzed to explain the ductile essences in the iridium compounds. Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)
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Open AccessArticle
First-Principles Assessment of the Structure and Stability of 15 Intrinsic Point Defects in Zinc-Blende Indium Arsenide
Crystals 2019, 9(1), 48; https://doi.org/10.3390/cryst9010048 - 17 Jan 2019
Cited by 1
Abstract
Point defects are inevitable, at least due to thermodynamics, and essential for engineering semiconductors. Herein, we investigate the formation and electronic structures of fifteen different kinds of intrinsic point defects of zinc blende indium arsenide (zb-InAs ) using first-principles calculations. For [...] Read more.
Point defects are inevitable, at least due to thermodynamics, and essential for engineering semiconductors. Herein, we investigate the formation and electronic structures of fifteen different kinds of intrinsic point defects of zinc blende indium arsenide (zb-InAs ) using first-principles calculations. For As-rich environment, substitutional point defects are the primary intrinsic point defects in zb-InAs until the n-type doping region with Fermi level above 0.32 eV is reached, where the dominant intrinsic point defects are changed to In vacancies. For In-rich environment, In tetrahedral interstitial has the lowest formation energy till n-type doped region with Fermi level 0.24 eV where substitutional point defects In A s take over. The dumbbell interstitials prefer < 110 > configurations. For tetrahedral interstitials, In atoms prefer 4-As tetrahedral site for both As-rich and In-rich environments until the Fermi level goes above 0.26 eV in n-type doped region, where In atoms acquire the same formation energy at both tetrahedral sites and the same charge state. This implies a fast diffusion along the t T t path among the tetrahedral sites for In atoms. The In vacancies V I n decrease quickly and monotonically with increasing Fermi level and has a q = 3 e charge state at the same time. The most popular vacancy-type defect is V I n in an As-rich environment, but switches to V A s in an In-rich environment at light p-doped region when Fermi level below 0.2 eV. This study sheds light on the relative stabilities of these intrinsic point defects, their concentrations and possible diffusions, which is expected useful in defect-engineering zb-InAs based semiconductors, as well as the material design for radiation-tolerant electronics. Full article
(This article belongs to the Special Issue First-Principles Prediction of Structures and Properties in Crystals)
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