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Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)

The present work applied the methods of density functional theory and the van der Waals interaction PBE + D3(BJ) on the basis of localized orbitals of the CRYSTAL17 package. It featured the effect of interactions between structural elements of fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr,...

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Autores principales: Zhuravlev, Yuri, Atuchin, Victor
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9607192/
https://www.ncbi.nlm.nih.gov/pubmed/36296432
http://dx.doi.org/10.3390/molecules27206840
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author Zhuravlev, Yuri
Atuchin, Victor
author_facet Zhuravlev, Yuri
Atuchin, Victor
author_sort Zhuravlev, Yuri
collection PubMed
description The present work applied the methods of density functional theory and the van der Waals interaction PBE + D3(BJ) on the basis of localized orbitals of the CRYSTAL17 package. It featured the effect of interactions between structural elements of fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd) on their elastic and vibrational properties. The hexagonal structures proved to consist of alternating ···B-CO(3)··· and ···A-F··· layers in planes ab, interconnected along axis c by infinite chains ···F-B-F···, where cations formed polyhedra AO(n)F(3) and BO(m)F(2). The calculations included the band energy structure, the total and partial density of electron states, the energy and band widths of the upper ns- and np-states of alkali and alkaline-earth metals, as well as nd-zinc and nd-cadmium. For hydrostatic compression, we calculated the parameters of the Birch–Murnaghan equation of state and the linear compressibility moduli along the crystal axes and bond lines. We also defined the elastic constants of single crystals to obtain the Voigt–Reuss–Hill approximations for the elastic moduli of polycrystalline materials. The study also revealed the relationship between the elastic properties and the nature of the chemical bond. Hybrid functional B3LYP made it possible to calculate the modes of normal long-wavelength oscillations, which provided the spectra of infrared absorption and Raman scattering. Intramolecular modes ν1 and ν4 with one or two maxima were found to be intense, and their relative positions depended on the lengths of nonequivalent C–O bonds.
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spelling pubmed-96071922022-10-28 Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd) Zhuravlev, Yuri Atuchin, Victor Molecules Article The present work applied the methods of density functional theory and the van der Waals interaction PBE + D3(BJ) on the basis of localized orbitals of the CRYSTAL17 package. It featured the effect of interactions between structural elements of fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd) on their elastic and vibrational properties. The hexagonal structures proved to consist of alternating ···B-CO(3)··· and ···A-F··· layers in planes ab, interconnected along axis c by infinite chains ···F-B-F···, where cations formed polyhedra AO(n)F(3) and BO(m)F(2). The calculations included the band energy structure, the total and partial density of electron states, the energy and band widths of the upper ns- and np-states of alkali and alkaline-earth metals, as well as nd-zinc and nd-cadmium. For hydrostatic compression, we calculated the parameters of the Birch–Murnaghan equation of state and the linear compressibility moduli along the crystal axes and bond lines. We also defined the elastic constants of single crystals to obtain the Voigt–Reuss–Hill approximations for the elastic moduli of polycrystalline materials. The study also revealed the relationship between the elastic properties and the nature of the chemical bond. Hybrid functional B3LYP made it possible to calculate the modes of normal long-wavelength oscillations, which provided the spectra of infrared absorption and Raman scattering. Intramolecular modes ν1 and ν4 with one or two maxima were found to be intense, and their relative positions depended on the lengths of nonequivalent C–O bonds. MDPI 2022-10-12 /pmc/articles/PMC9607192/ /pubmed/36296432 http://dx.doi.org/10.3390/molecules27206840 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Zhuravlev, Yuri
Atuchin, Victor
Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)
title Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)
title_full Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)
title_fullStr Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)
title_full_unstemmed Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)
title_short Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO(3)F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)
title_sort chemical bonding effects and physical properties of noncentrosymmetric hexagonal fluorocarbonates abco(3)f (a: k, rb, cs; b: mg, ca, sr, zn, cd)
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9607192/
https://www.ncbi.nlm.nih.gov/pubmed/36296432
http://dx.doi.org/10.3390/molecules27206840
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