Pressure-Induced Structural Transformations and Electronic Transitions in TeO2 Glass by Raman Spectroscopy

Anastasios G. Papadopoulos; Nagia S. Tagiara; Elissaios Stavrou; Fei Li; Guochun Yang; Efstratios I. Kamitsos

doi:10.1021/acs.jpclett.2c03612

Pressure-Induced Structural Transformations and Electronic Transitions in TeO₂ Glass by Raman Spectroscopy

Anastasios G. Papadopoulos, Nagia S. Tagiara, Elissaios Stavrou^*, Fei Li, Guochun Yang, Efstratios I. Kamitsos^*

^*Corresponding author for this work

Materials Science and Engineering

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

1 Scopus citations

Abstract

TeO2 glass has been studied by Raman spectroscopy up to the record pressure of 70 GPa. The boson peak frequency ωb exhibits a decrease of the Ã¢Â?Â?ωb/Ã¢Â?Â?P slope at 5-6 GPa and saturates above 30 GPa with a practically constant value up to 70 GPa. Experiment and theory indicate that pressures up to 20 GPa induce the transformation of single Te-O-Te bridges to double Te-O2-Te bridges, leading to a more compact structure, while Raman activity developing at higher pressures around 580 cm-1 signals the increase of Te coordination from 4- to 6-fold. Natural bond orbital analysis shows that double Te-O2-Te bridges favor the s → d transition and promote the increase of Te coordination through d2sp3 hybridization. This transition leads to the formation of TeO6 octahedra, in strict difference with crystalline TeO2 at the same pressure range, and to the development of a 3D network that freezes the medium range order.

Original language	English
Journal	Journal of Physical Chemistry Letters
DOIs	https://doi.org/10.1021/acs.jpclett.2c03612
State	Published - 9 Jan 2023

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@article{f5f981f8b19a48c48d64d29c2cd5d914,

title = "Pressure-Induced Structural Transformations and Electronic Transitions in TeO2 Glass by Raman Spectroscopy",

abstract = "TeO2 glass has been studied by Raman spectroscopy up to the record pressure of 70 GPa. The boson peak frequency ωb exhibits a decrease of the {\~A}¢{\^A}?{\^A}?ωb/{\~A}¢{\^A}?{\^A}?P slope at 5-6 GPa and saturates above 30 GPa with a practically constant value up to 70 GPa. Experiment and theory indicate that pressures up to 20 GPa induce the transformation of single Te-O-Te bridges to double Te-O2-Te bridges, leading to a more compact structure, while Raman activity developing at higher pressures around 580 cm-1 signals the increase of Te coordination from 4- to 6-fold. Natural bond orbital analysis shows that double Te-O2-Te bridges favor the s → d transition and promote the increase of Te coordination through d2sp3 hybridization. This transition leads to the formation of TeO6 octahedra, in strict difference with crystalline TeO2 at the same pressure range, and to the development of a 3D network that freezes the medium range order.",

author = "Papadopoulos, {Anastasios G.} and Tagiara, {Nagia S.} and Elissaios Stavrou and Fei Li and Guochun Yang and Kamitsos, {Efstratios I.}",

year = "2023",

month = jan,

day = "9",

doi = "10.1021/acs.jpclett.2c03612",

language = "英语",

journal = "Journal of Physical Chemistry Letters",

issn = "1948-7185",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Pressure-Induced Structural Transformations and Electronic Transitions in TeO2 Glass by Raman Spectroscopy

AU - Papadopoulos, Anastasios G.

AU - Tagiara, Nagia S.

AU - Stavrou, Elissaios

AU - Li, Fei

AU - Yang, Guochun

AU - Kamitsos, Efstratios I.

PY - 2023/1/9

Y1 - 2023/1/9

N2 - TeO2 glass has been studied by Raman spectroscopy up to the record pressure of 70 GPa. The boson peak frequency ωb exhibits a decrease of the Ã¢Â?Â?ωb/Ã¢Â?Â?P slope at 5-6 GPa and saturates above 30 GPa with a practically constant value up to 70 GPa. Experiment and theory indicate that pressures up to 20 GPa induce the transformation of single Te-O-Te bridges to double Te-O2-Te bridges, leading to a more compact structure, while Raman activity developing at higher pressures around 580 cm-1 signals the increase of Te coordination from 4- to 6-fold. Natural bond orbital analysis shows that double Te-O2-Te bridges favor the s → d transition and promote the increase of Te coordination through d2sp3 hybridization. This transition leads to the formation of TeO6 octahedra, in strict difference with crystalline TeO2 at the same pressure range, and to the development of a 3D network that freezes the medium range order.

AB - TeO2 glass has been studied by Raman spectroscopy up to the record pressure of 70 GPa. The boson peak frequency ωb exhibits a decrease of the Ã¢Â?Â?ωb/Ã¢Â?Â?P slope at 5-6 GPa and saturates above 30 GPa with a practically constant value up to 70 GPa. Experiment and theory indicate that pressures up to 20 GPa induce the transformation of single Te-O-Te bridges to double Te-O2-Te bridges, leading to a more compact structure, while Raman activity developing at higher pressures around 580 cm-1 signals the increase of Te coordination from 4- to 6-fold. Natural bond orbital analysis shows that double Te-O2-Te bridges favor the s → d transition and promote the increase of Te coordination through d2sp3 hybridization. This transition leads to the formation of TeO6 octahedra, in strict difference with crystalline TeO2 at the same pressure range, and to the development of a 3D network that freezes the medium range order.

U2 - 10.1021/acs.jpclett.2c03612

DO - 10.1021/acs.jpclett.2c03612

M3 - 文章

C2 - 36622290

SN - 1948-7185

JO - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

ER -

Pressure-Induced Structural Transformations and Electronic Transitions in TeO2 Glass by Raman Spectroscopy

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Pressure-Induced Structural Transformations and Electronic Transitions in TeO₂ Glass by Raman Spectroscopy