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

Deniss Grjaznovs; Linas Vilčiauskas

doi:10.3390/ma16124361

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

Deniss Grjaznovs^*
, Linas Vilčiauskas^*

^*Corresponding author for this work

Center for Physical Sciences and Technology

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

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 (Formula presented.) space group and averaged vanadium oxidation states of V (Formula presented.) in the ground state, whereas K₄V₂(PO₄)₃ adopted a monoclinic structure with the (Formula presented.) space group and mixed vanadium oxidation states V (Formula presented.) /V (Formula presented.) 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 (Formula presented.) 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.

Original language	English
Article number	4361
Pages (from-to)	1-11
Journal	Materials
Volume	16
Issue number	12
DOIs	https://doi.org/10.3390/ma16124361
Publication status	Published - Jun 2023

Keywords

density functional theory
hybrid-exchange-correlation functionals
NASICON
sodium vanadium phopshate

OECD Field of Science

1.3 Physical Sciences

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10.3390/ma16124361

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

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 (Formula presented.) space group and averaged vanadium oxidation states of V (Formula presented.) in the ground state, whereas K4V2(PO4)3 adopted a monoclinic structure with the (Formula presented.) space group and mixed vanadium oxidation states V (Formula presented.) /V (Formula presented.) 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 (Formula presented.) 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.",

keywords = "density functional theory, hybrid-exchange-correlation functionals, NASICON, sodium vanadium phopshate",

author = "Deniss Grjaznovs and Linas Vil{\v c}iauskas",

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T1 - On the Symmetry, Electronic Properties, and Possible Metallic States in NASICON-Structured A4V2(PO4)3 (A = Li, Na, K) Phosphates

AU - Grjaznovs, Deniss

AU - Vilčiauskas, Linas

PY - 2023/6

Y1 - 2023/6

N2 - 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 (Formula presented.) space group and averaged vanadium oxidation states of V (Formula presented.) in the ground state, whereas K4V2(PO4)3 adopted a monoclinic structure with the (Formula presented.) space group and mixed vanadium oxidation states V (Formula presented.) /V (Formula presented.) 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 (Formula presented.) 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.

AB - 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 (Formula presented.) space group and averaged vanadium oxidation states of V (Formula presented.) in the ground state, whereas K4V2(PO4)3 adopted a monoclinic structure with the (Formula presented.) space group and mixed vanadium oxidation states V (Formula presented.) /V (Formula presented.) 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 (Formula presented.) 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.

KW - density functional theory

KW - hybrid-exchange-correlation functionals

KW - NASICON

KW - sodium vanadium phopshate

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U2 - 10.3390/ma16124361

DO - 10.3390/ma16124361

M3 - Article

SN - 1996-1944

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SP - 1

EP - 11

JO - Materials

JF - Materials

IS - 12

M1 - 4361

ER -

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

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