Radioelectronics and radioelectronic equipment manufacturing

First-Principle Study of Electronic Structure and Atomic Architecture of Vanadate Apatites of Calcium and Cadmium

Authors

A. P. Soroka
Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv
V. H. Kasianenko
Ivano-Frankivsk National Technical University of Oil and Gas ROR , Vinnytsia National Technical University ROR
I. V. Suhenko
Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv
L. I. Karbivska
Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv
V. L. Karbivskii
Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv
O. I. Sobolev
Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv
DOI https://doi.org/10.31649/1997-9266-2024-177-6-161-171

Keywords

density functional theory apatite electronic structure Bader analysis atomic structure

Abstract

The electronic structure of the apatite series Me10(VO4)6X2, where Me represents calcium (Ca) or cadmium (Cd) and X denotes fluoride (F), chloride (Cl), or hydroxide (OH), was computed through first principles within the framework of electron density functional theory (DFT). This calculation utilized the full-potential all-electron APW method, supplemented by a set of basis functions (APW + lo). The generalized gradient approximation (GGA) was employed for the exchange-correlation component of the potential, specifically the PBE (Perdew, Burke, Ernzerhof) functional, which is widely recognized in GGA applications. To achieve convergence in the computational results, we examined the dependency on k-grids during structural relaxation, ultimately determining that a 2–2–3 Monkhorst-Pack k-grid centered at the Γ point yields optimal results. The atomic position relaxation for the compounds Me10(VO4)6X2 (Me = Ca or Cd; X = F, Cl, OH) was conducted within the space group P63/m. For the specific compounds Ca10(VO4)6(OH)2 and Cd10(VO4)6(OH)2, we employed the P63 group. The reduction in symmetry observed in hydroxyapatites, in contrast to chloro- and fluoroapatites, is attributed to the incorporation of two additional hydrogen atoms along the c-axis. This alteration results in a symmetry violation concerning the mirror planes that are perpendicular to the axis intersecting the points (0, 0, 0.25) and (0, 0, 0.75).

Bader analysis was performed to elucidate the nature of the chemical bonding. We assessed the evolution of the electronic energy structure within the valence and forbidden bands for the aforementioned apatite series. Additionally, we calculated the parameters associated with the unit cells of these apatites. Our findings indicate that the "near-Fermi" region of the total densities of states is predominantly influenced by the electronic states of oxygen (2p) and cadmium (4d) states within the cadmium apatites. The subvalence states are primarily derived from the 2s states of oxygen. The electronic 3d states of vanadium exhibit a minimal contribution to the "near-Fermi" region, while the bottom of the conduction band is chiefly formed by the calcium (3d) and vanadium (3d) states. Furthermore, we established that the V―O bond is primarily dictated by a strong interaction between O 2p and V 3d states.

Notably, as the electronegativity of the anion X (F, Cl, OH) decreases, the gap width exhibits a slight reduction of a few tenths of an electron volt. On the other hand, substituting calcium with cadmium leads to a significant decrease in the gap width of approximately 0.6 electron volts.

Thus, density functional theory (DFT) with exchange-correlation potential PBE makes it possible to accurately calculate the lattice parameters for calcium and cadmium apatites and the band gap widths for calcium apatites. However, a significant reduction in the gap width when calcium atoms are replaced for cadmium still requires experimental confirmation.

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How to Cite

[1]
“First-Principle Study of Electronic Structure and Atomic Architecture of Vanadate Apatites of Calcium and Cadmium”, Вісник ВПІ, no. 6, pp. 161–171, Dec. 2024, doi: 10.31649/1997-9266-2024-177-6-161-171.

Author Biographies

A. P. Soroka, Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv

Cand. Sc. (Eng.), Senior Research Scientist

V. H. Kasianenko, Ivano-Frankivsk National Technical University of Oil and Gas, Vinnytsia National Technical University

Dr. Sc. (Eng.), Head of the Chair of General Physics

I. V. Suhenko, Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv

Post-Graduate Student of the Department of “Physics of nanostructures”

L. I. Karbivska, Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv

Dr. Sc. (Eng.), Lead Researcher of the Institute of Metal Physics

V. L. Karbivskii, Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv

Dr. Sc. (Eng.), Head of the Department of «Physics of nanostructures»

O. I. Sobolev, Kurdyumov Institute for Metal Physics of the NAS of Ukraine, Kyiv

Junior Researcher of the Institute for Metal Physics

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