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Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Materials Simulation and Design".

Deadline for manuscript submissions: 10 July 2024 | Viewed by 8019

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Special Issue Editors

Dr. Denis Gryaznov

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Guest Editor

Institute of Solid State Physics, University of Latvia, Riga, Latvia
Interests: electrode; lithium and sodium batteries; solid oxide cells; DFT calculations; group theory

Dr. Eugene Kotomin

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Guest Editor

1. Institute of Solid State Physics, University of Latvia, Riga, Latvia
2. Max Planck Institute for Solid State Research, Stuttgart, Germany
Interests: first principles calculations of surfaces and defects; hybrid functionals; oxide and perovskite materials; nanomaterials; solid oxide fuel cells; photostimulated water splitting; radiation damage; scintillators and dodimeters; kinetics of defect-induced reactions

Prof. Dr. Roberto Dovesi

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Guest Editor

Department of Chemistry, University of Turin, Turin, Italy
Interests: quantum mechanical simulation of solids; transition metal compouds; perovskites; EPR; IR and Raman spectra

Special Issue Information

Dear Colleagues,

Density functional theory (DFT) is nowadays playing a crucial role in materials science and related disciplines. It mainly lays in its ability to accurately predict many materials properties and/or materials behavior under different external conditions, bringing closer two important communities, i.e., theoreticians and experimentalists. It has become possible due to constantly ongoing developments in DFT and related theoretical methods as well as modern capabilities of high-performance computing facilities to predict materials properties, demanding a comparison between modelling and experimental results. In this sense ‘computational experiment [1-3]’ is able to replace the real experiment, which cannot be undertaken for hazardous or radioactive materials, or due to high expenses. Often, ‘computational experiment’ supports the real experiments with deeper understanding of observed phenomena at atomistic scale. Thus, the present special issue aims at combining analysis of advanced materials modelling and experimental results. We, therefore, expect contributions from theoreticians using a careful comparison of their results for materials properties with experimental data as well as experimentalists and theoreticians critically comparing their experimental and modelling results. Computed properties of all kinds of crystals could include (et non solum):

Vibrational properties and spectra
Optical properties and spectra
Mechanical, piezoelectric and dielectric properties
X-ray spectra
Magnetic properties and structures
Defects structures and energetics: defects formation and migration energy
Electron paramagnetic resonance
Thermoelectric properties: Seebeck coefficient, electrical conductivity
Thermodynamics and phase diagrams

In addition, use of two or more DFT methods, for example, plane waves and Gaussian-type basis and/or different exchange-correlation functionals, is advantageous for the DFT developments, proper understanding of computed properties and is, therefore, leading to more sophisticated comparison with or replacement of experiments. Relevant contributions are especially welcome.

[1] P.J. Hasnip, K. Refson, M.I. Probert, J. R. Yates, S. J. Clark, C. J. Pickard, “Density functional theory in the solid state”, Philosophical Transactions of the Royal Society A 372, 20130270 (2014).

[2] P. Makkar, N. N. GHosh, “A review on the use of DFT for the prediction of the properties of nanomaterials”, RSC Advances 11, 27897 (2021).

[3] A. Erba, J. Baima, I. Bush, R. Orlando, R. Dovesi, “Large scale Condensed Matter DFT Simulations” Performance and Capabilities of CRYSTAL code”, J. Chem. Theory Comput. 13 (10), 5019-5027 (2017).

Dr. Denis Gryaznov
Dr. Eugene Kotomin
Prof. Dr. Roberto Dovesi
Guest Editors

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Keywords

first principles calculations
exchange-correlation functional
DFPT
TD-DFT
excited states
crystals
surfaces
polarons
defects
comparison

Published Papers (7 papers)

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Research

20 pages, 5656 KiB

Open AccessArticle

Electronic, Optical, and Vibrational Properties of an AgAlS₂ Crystal in a High-Pressure Phase

by Myron Ya. Rudysh, Anatolii O. Fedorchuk, Mikhail G. Brik, Jurij Grechenkov, Dmitry Bocharov, Sergei Piskunov, Anatoli I. Popov and Michal Piasecki

Materials 2023, 16(21), 7017; https://doi.org/10.3390/ma16217017 - 02 Nov 2023

Viewed by 760

Abstract

The aim of this study is to comprehensively examine the structural composition and properties of the AgAlS₂ crystal during its high-pressure phase. This analysis delves into the second coordination environment of the crystal structure and elucidates the distinct transformations it undergoes during the phase transition. The band energy structure was calculated, and the origin of electronic levels was clarified. It is shown that the crystal becomes non-stratified during the phase transition. This study also determined the values of the crystal’s carrier effective masses, underscoring its spatial anisotropy. It was found that the calculated optical functions are similar to the crystal in the chalcopyrite structure, and their differences are shown. Further, this study involved the calculation of the crystal’s phonon spectrum, revealing the spectrum’s transformation during the phase transition. The vibrational frequencies were also obtained, with a symmetrical classification of vibrational modes. Finally, this study derived the infrared and Raman spectra of the AgAlS₂ crystal, thereby providing a comprehensive picture of the crystal during its high-pressure phase. Full article

(This article belongs to the Special Issue Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments)

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15 pages, 1270 KiB

Open AccessArticle

Modeling of the Lattice Dynamics in Strontium Titanate Films of Various Thicknesses: Raman Scattering Studies

by Veera Krasnenko, Alexander Platonenko, Aleksandr Liivand, Leonid L. Rusevich, Yuri A. Mastrikov, Guntars Zvejnieks, Maksim Sokolov and Eugene A. Kotomin

Materials 2023, 16(18), 6207; https://doi.org/10.3390/ma16186207 - 14 Sep 2023

Cited by 1 | Viewed by 813

Abstract

While the bulk strontium titanate (STO) crystal characteristics are relatively well known, ultrathin perovskites’ nanostructure, chemical composition, and crystallinity are quite complex and challenging to understand in detail. In our study, the DFT methods were used for modelling the Raman spectra of the STO bulk (space group I4/mcm) and 5–21-layer thin films (layer group p4/mbm) in tetragonal phase with different thicknesses ranging from ~0.8 to 3.9 nm. Our calculations revealed features in the Raman spectra of the films that were absent in the bulk spectra. Out of the seven Raman-active modes associated with bulk STO, the frequencies of five modes (2E_g, A_1g, B_2g, and B_1g) decreased as the film thickness increased, while the low-frequency B_2g and higher-frequency E_g modes frequencies increased. The modes in the films exhibited vibrations with different amplitudes in the central or surface parts of the films compared to the bulk, resulting in frequency shifts. Some peaks related to bulk vibrations were too weak (compared to the new modes related to films) to distinguish in the Raman spectra. However, as the film thickness increased, the Raman modes approached the frequencies of the bulk, and their intensities became higher, making them more noticeable in the Raman spectrum. Our results could help to explain inconsistencies in the experimental data for thin STO films, providing insights into the behavior of Raman modes and their relationship with film thickness. Full article

(This article belongs to the Special Issue Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments)

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20 pages, 3751 KiB

Open AccessEditor’s ChoiceArticle

Molecular Mechanism of the Piezoelectric Response in the β-Phase PVDF Crystals Interpreted by Periodic Boundary Conditions DFT Calculations

by Gianluca Serra, Alessia Arrigoni, Mirella Del Zoppo, Chiara Castiglioni and Matteo Tommasini

Materials 2023, 16(17), 6004; https://doi.org/10.3390/ma16176004 - 31 Aug 2023

Viewed by 981

Abstract

A theoretical approach based on Periodic Boundary Conditions (PBC) and a Linear Combination of Atomic Orbitals (LCAO) in the framework of the density functional theory (DFT) is used to investigate the molecular mechanism that rules the piezoelectric behavior of poly(vinylidene fluoride) (PVDF) polymer in the crystalline β-phase. We present several computational tests highlighting the peculiar electrostatic potential energy landscape the polymer chains feel when they change their orientation by a rigid rotation in the lattice cell. We demonstrate that a rotation of the permanent dipole through chain rotation has a rather low energy cost and leads to a lattice relaxation. This justifies the macroscopic strain observed when the material is subjected to an electric field. Moreover, we investigate the effect on the molecular geometry of the expansion of the lattice parameters in the (a, b) plane, proving that the rotation of the dipole can take place spontaneously under mechanical deformation. By band deconvolution of the IR and Raman spectra of a PVDF film with a high content of β-phase, we provide the experimental phonon wavenumbers and relative band intensities, which we compare against the predictions from DFT calculations. This analysis shows the reliability of the LCAO approach, as implemented in the CRYSTAL software, for calculating the vibrational spectra. Finally, we investigate how the IR/Raman spectra evolve as a function of inter-chain distance, moving towards the isolated chain limit and to the limit of a single crystal slab. The results show the relevance of the inter-molecular interactions on the vibrational dynamics and on the electro-optical features ruling the intensity pattern of the vibrational spectra. Full article

(This article belongs to the Special Issue Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments)

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11 pages, 660 KiB

Open AccessArticle

On the Symmetry, Electronic Properties, and Possible Metallic States in NASICON-Structured A₄V₂(PO₄)₃ (A = Li, Na, K) Phosphates

by Denis Gryaznov and Linas Vilčiauskas

Materials 2023, 16(12), 4361; https://doi.org/10.3390/ma16124361 - 13 Jun 2023

Viewed by 803

Abstract

In this work, the electronic structure and properties of NASICON-structured A₄V₂(PO₄)₃, where A = Li, Na, K were studied using hybrid density functional theory calculations. The symmetries were analyzed using a group theoretical approach, and the band structures were examined by the atom and orbital projected density of states analyses. Li₄V₂(PO₄)₃ and Na₄V₂(PO₄)₃ adopted monoclinic structures with the

C 2

space group and averaged vanadium oxidation states of V

^{+ 2.5}

in the ground state, whereas K₄V₂(PO₄)₃ adopted a monoclinic structure with the

C 2

space group and mixed vanadium oxidation states V

^{+ 2}

^{+ 3}

in the ground state. The mixed oxidation state is the least stable state in Na₄V₂(PO₄)₃ and Li₄V₂(PO₄)₃. Symmetry increases in Li₄V₂(PO₄)₃ and Na₄V₂(PO₄)₃ led to the appearance of a metallic state that was independent of the vanadium oxidation states (except for the averaged oxidation state

R 32

Na₄V₂(PO₄)₃). On the other hand, K₄V₂(PO₄)₃ retained a small band gap in all studied configurations. These results might provide valuable guidance for crystallography and electronic structure investigations for this important class of materials. Full article

(This article belongs to the Special Issue Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments)

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12 pages, 6641 KiB

Open AccessArticle

The Electronic Structures and Energies of the Lowest Excited States of the N_s⁰, N_s⁺, N_s⁻ and N_s-H Defects in Diamond

by Alexander Platonenko, William C. Mackrodt and Roberto Dovesi

Materials 2023, 16(5), 1979; https://doi.org/10.3390/ma16051979 - 28 Feb 2023

Cited by 1 | Viewed by 1162

Abstract

This paper reports the energies and charge and spin distributions of the mono-substituted N defects, N⁰_s, N⁺_s, N⁻_s and N_s-H in diamonds from direct Δ-SCF calculations based on Gaussian orbitals within the B3LYP function. These predict that (i) N_s⁰, N_s⁺ and N_s⁻ all absorb in the region of the strong optical absorption at 270 nm (4.59 eV) reported by Khan et al., with the individual contributions dependent on the experimental conditions; (ii) N_s-H, or some other impurity, is responsible for the weak optical peak at 360 nm (3.44 eV); and that N_s⁺ is the source of the 520 nm (2.38 eV) absorption. All excitations below the absorption edge of the diamond host are predicted to be excitonic, with substantial re-distributions of charge and spin. The present calculations support the suggestion by Jones et al. that N_s⁺ contributes to, and in the absence of N_s⁰ is responsible for, the 4.59 eV optical absorption in N-doped diamonds. The semi-conductivity of the N-doped diamond is predicted to rise from a spin-flip thermal excitation of a CN hybrid orbital of the donor band resulting from multiple in-elastic phonon scattering. Calculations of the self-trapped exciton in the vicinity of N_s⁰ indicate that it is essentially a local defect consisting of an N and four nn C atoms, and that beyond these the host lattice is essential a pristine diamond as predicted by Ferrari et al. from the calculated EPR hyperfine constants. Full article

(This article belongs to the Special Issue Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments)

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26 pages, 1407 KiB

Open AccessArticle

The d Orbital Multi Pattern Occupancy in a Partially Filled d Shell: The KFeF₃ Perovskite as a Test Case

by Fabien Pascale, Sami Mustapha, Philippe D’Arco and Roberto Dovesi

Materials 2023, 16(4), 1532; https://doi.org/10.3390/ma16041532 - 12 Feb 2023

Cited by 4 | Viewed by 1088

Abstract

The occupancy of the d shell in KFeF

_{3}

t_{2 g}^{4}

_{g}^{2}

, with five

α

and one

β

electrons. The Jahn–Teller lift of degeneracy in the

t_{2 g}

sub-shell produces a tetragonal relaxation of the unit [...] Read more.

The occupancy of the d shell in KFeF

_{3}

t_{2 g}^{4}

_{g}^{2}

, with five

α

and one

β

electrons. The Jahn–Teller lift of degeneracy in the

t_{2 g}

sub-shell produces a tetragonal relaxation of the unit cell (4.09 vs. 4.22 Å, B3LYP result) not observed experimentally. In order to understand the origin of this apparent contradiction, we explored, with a 2 × 2 × 2 supercell (40 atoms per cell), all possible local structures in which contiguous Fe atoms have a different occupancy of the

t_{2 g}

orbitals with the minority spin electron. A total of 6561 configurations (with occupancies from (8,0,0) to (3,2,2) of the 3

t_{2 g}

orbitals of the 8 Fe atoms) have been explored, with energies in many cases lower (by up to 1550

μ

_{h}

per 2 Fe atoms) than the one of the fully ordered case, both for the ferromagnetic and the anti-ferromagnetic solutions. The results confirm that the orientation of the

β

d electron of Fe influences the electrostatics (more efficient relative orientation of the Fe quadrupoles of the d shell) of the system, but not the magnetic interactions. Three hybrid functionals, B3LYP, PBE0, and HSE06, provide very similar results. Full article

(This article belongs to the Special Issue Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments)

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17 pages, 1588 KiB

Open AccessArticle

Difference in Structure and Electronic Properties of Oxygen Vacancies in α-Quartz and α-Cristobalite Phases of SiO₂

by Katherine L. Milton, Thomas R. Durrant, Teofilo Cobos Freire and Alexander L. Shluger

Materials 2023, 16(4), 1382; https://doi.org/10.3390/ma16041382 - 07 Feb 2023

Cited by 4 | Viewed by 1735

Abstract

α

-cristobalite (

α

-C) is a polymorph of silica, mainly found in space exploration and geochemistry research. Due to similar densities,

α

-C is often used as a proxy for amorphous SiO

_{2}

, particularly in computer simulations of SiO

_{2}

surfaces [...] Read more.

α

-cristobalite (

α

-C) is a polymorph of silica, mainly found in space exploration and geochemistry research. Due to similar densities,

α

-C is often used as a proxy for amorphous SiO

_{2}

, particularly in computer simulations of SiO

_{2}

surfaces and interfaces. However, little is known about the properties of

α

-C and its basic oxygen defects. Using density functional theory (DFT) simulations we provide a comprehensive report on the properties of perfect structure and oxygen vacancies in

α

-C. The calculated properties of

α

-C are compared with those of the better-characterized

α

-quartz (

α

-Q). Our results demonstrated that the positively charged O vacancy in

α

-C is most stable in the dimer configuration, in contrast to

α

-Q, which favors the puckered configuration. A back-projected configuration was also predicted in both polymorphs. We calculated the optical transition energies and isotropic hyperfine constants for O vacancies in both

α

-Q and

α

-C, and compared our findings with the results of previous studies and experiments. This work, thus, offers one of the first in-depth investigations of the properties of oxygen vacancies in

α

-C. Full article

(This article belongs to the Special Issue Density Functional Theory and Its Applications in Materials Science: A Critical Comparison between Theoretical Modelling of Crystals and Experiments)

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