Comparative Analysis of the Electronic Structure and Nonlinear Optical Susceptibility of α-TeO<sub>2</sub> and β-TeO<sub>3</sub> Crystals

Roginskiĭ, E. M.; Кузнецов, В. Г.; Smirnov, M. B.; Noguera, Olivier; Duclère, Jean‐René; Colas, Maggy; Masson, Olivier; Thomas, Philippe

doi:10.1021/acs.jpcc.7b01819

Cited by 20 publications

(21 citation statements)

References 59 publications

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“…From the optical properties viewpoint, the high linear and nonlinear optical indices of TeO 2based glasses have been associated with the presence of the Te 4+ lone electron pair [6][7][8][9][10] and characteristic Te-O-Te bridges [3,[11][12][13]. It has been shown that this inherently high optical response can be further improved upon adding transition metal oxides of empty d-orbital cations, such as titanium oxide TiO 2 or tungsten oxide WO 3 [14,15].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system

Zaki

Hamani

Colas

et al. 2018

Journal of Non-Crystalline Solids

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et al.. Synthesis, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system. Abstract.The glass-forming domain and physical properties, namely, the density, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system have been investigated. By means of micro-Raman spectroscopy, the structure of these glasses was examined based on a full-scale spectral decomposition. The optical transmission and refractive index dispersion were measured by UV-Vis-NIR spectroscopy and spectroscopic ellipsometry respectively. Consistent correlations were established between the structural and linear optical properties. Only minor structural modifications of the original TeO2-rich network are taking place upon adding TiO2 or WO3, suggesting the absence of Te-O-Te bond network depolymerization. Our results also suggest that, upon increasing TiO2 content, a phase separation occurs between amorphous TeO2-rich and amorphous TiO2-rich regions. We also argue that the structural trends upon adding WO3 evolve from uniformly dispersed WO6 octahedra (at low WO3 content) to amorphous WO3-like regions (at higher WO3 content) before the crystallization of γ-WO3 at 30 mol.% of WO3. The compositional dependence of the refractive index and several optical constants (Urbach EU and dispersion Ed energies, oxide ion polarizabilities) is highlighted. These glasses collectively exhibit high refractive indices in the order of ~2.2. Graphical abstract. Highlights. New glass-forming domain within the TeO 2 -TiO 2 -WO 3 system was determined. Relevant correlations between the structural and optical properties are established. Structural effects of TiO 2 and WO 3 are revealed and discussed in detail. The investigated glasses exhibit high refractive indices in the order of ~2.2. Keywords.Tellurite glasses; glass structure; Raman spectroscopy; linear optical properties.is found that upon adding WO 3 from 5 to 25 mol.%, α O2-slightly increases from ~1.6 to ~1.8 Å 3 while remaining practically constant with addition of TiO 2 . This slight increase of α O2-values indicates that the overall glass network becomes slightly more "polarized", and thus a little more ionic in nature. Conclusions.A new TeO 2 -based glass-forming domain has been explored and investigated within the ternary TeO 2 -TiO 2 -WO 3 system. Density, thermal, structural and linear optical properties have been measured and analyzed as a function of TiO 2 and WO 3 contents.The structural properties of TTxWy glasses were examined using micro-Raman spectroscopy to highlight the structural roles and effects of adding TiO 2 and WO 3 on the short-to mediumrange structure. We report the following structural trends:  Globally, only minor structural modifications are taking place upon adding TiO 2 or WO 3 , (i) indicating that TTxWy glasses collectively share common features of the pure TeO 2 glass network and (ii) suggesting the absence of Te-O-Te bond network depolymerization (induced transformation of TeO 4 into TeO 3 units)...

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Section: Introductionmentioning

confidence: 99%

Synthesis, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system

Zaki

Hamani

Colas

et al. 2018

Journal of Non-Crystalline Solids

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“…С целью более корректного учета локализации 5d-электронов на атомах теллура в расчетах учитывались поправки Хаббарда к функционалу плотности (схема LDA + U) [10]. Значение параметра U было позаимствовано из статьи [11] для α-фазы парателлурита ввиду близости структурного строения. Оптимизированные нелокальные (с двумя проекторами нелокальной части) сохраняющие норму псевдопотенциалы для атомов Te и O, использовались в настоящих расчетах [12].…”

Section: техника вычисленийunclassified

“…Как было показано ранее [11], точность предсказания нелинейных оптических свойств сильно зависит от точности предсказания электронной структуры кристалла. К сожалению, до сих пор ширина запрещенной зоны γ-TeO 2 не определена экспериментально.…”

Section: электронная структура и анализ химической связиunclassified

Электронная структура и нелинейная диэлектрическая восприимчивость γ-фазы оксида теллура

Рогинский¹,

Смирнов²

2020

Физика Твердого Тела

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The structural electronic and nonlinear optical properies of the γ-TeO2 crystal is studied by ab inito quantum mechanical calculations. The incluence of 5d electrons localization effect is taken into account in calculations by using Habbard-like correction term (LDA+U approximation). The obtained within such approach structural parameters are obtained in a good agreement with experimental data. The electronic bund structure is studied within quasiparticle G0W0 approximation, which is known as the most accurate method. It was found that the γ-TeO2 crystal is wide gap semiconductor with non-direct band gap. The analysis of the chemical bond is performed using Maximaly Localized Wannier functions. It is established that the valence electrons of ozigen atoms are belong to sp3-hybridization states and valence of tellurium atoms are equal to four.

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“…As an example, the nonlinear optical properties of tellurite (i.e. TeO 2 -based) materials are known to be partly caused by the activity of the 5s 2 LP of Te 4+ cations (Fargin et al, 1996;Jeansannetas et al, 1999;Suehara et al, 2004a,b;Soulis et al, 2008;Roginskii et al, 2017). The position and steric effect of LPs are thus valuable parameters for understanding the structure-properties relationships of some inorganic compounds and must be assessed by experimental or theoretical methods.…”

Section: Introductionmentioning

confidence: 99%

Localization and steric effect of the lone electron pair of the tellurium Te⁴⁺cation and other cations of thep-block elements. A systematic study

2020

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A simple method has been developed based on pure geometrical concepts to localize lone pairs (LPs) of cations of the p-block elements and model their steric effect. The method was applied to 1185 structures containing LP cations in 2439 non-equivalent positions. For oxide crystal structures, it is observed that, going from bottom left to top right in the periodic table, LPs move away from the cation core and decrease in size. For a given kind of cation M*, the LP radius increases linearly with the M*–LP distance, the smallest rate being observed for Tl+ and the largest for Cl5+. The influence of the anion type was also studied in the case of the Te4+ cation. Overall, the same trends were observed. The smallest Te–LP distances and LP radii are found for anions of large size and small charge.

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Comparative Analysis of the Electronic Structure and Nonlinear Optical Susceptibility of α-TeO₂ and β-TeO₃ Crystals

Cited by 20 publications

References 59 publications

Synthesis, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system

Synthesis, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system

Электронная структура и нелинейная диэлектрическая восприимчивость γ-фазы оксида теллура

Localization and steric effect of the lone electron pair of the tellurium Te⁴⁺cation and other cations of thep-block elements. A systematic study

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Comparative Analysis of the Electronic Structure and Nonlinear Optical Susceptibility of α-TeO2 and β-TeO3 Crystals

Cited by 20 publications

References 59 publications

Synthesis, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system

Synthesis, thermal, structural and linear optical properties of new glasses within the TeO2-TiO2-WO3 system

Электронная структура и нелинейная диэлектрическая восприимчивость &gamma;-фазы оксида теллура

Localization and steric effect of the lone electron pair of the tellurium Te4+cation and other cations of thep-block elements. A systematic study

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Comparative Analysis of the Electronic Structure and Nonlinear Optical Susceptibility of α-TeO₂ and β-TeO₃ Crystals

Электронная структура и нелинейная диэлектрическая восприимчивость γ-фазы оксида теллура

Localization and steric effect of the lone electron pair of the tellurium Te⁴⁺cation and other cations of thep-block elements. A systematic study