A STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPY

The room-temperature diffuse-reflectance spectra of compositions within the Li1+xTi2-xO4 spinel system (0 ≤ x ≤ 1 3) show three absorption bands in the range 4000 to 48,000 cm-1. Two high-energy absorption bands correspond to charge-transfer transitions from the oxygen-2p valence band to the titaniu...

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Main Authors: Harrison, M, Edwards, P, Goodenough, J
Format: Journal article
Language:English
Published: 1984
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author Harrison, M
Edwards, P
Goodenough, J
author_facet Harrison, M
Edwards, P
Goodenough, J
author_sort Harrison, M
collection OXFORD
description The room-temperature diffuse-reflectance spectra of compositions within the Li1+xTi2-xO4 spinel system (0 ≤ x ≤ 1 3) show three absorption bands in the range 4000 to 48,000 cm-1. Two high-energy absorption bands correspond to charge-transfer transitions from the oxygen-2p valence band to the titanium t2g and σ* conduction bands, where the σ* band of eg character has hybridized titanium-3d and titanium-4s parentage. The absorption band arising from promotion of electrons to the empty σ* band does not alter with composition whereas the absorption band arising from promotion of electrons to the partially filled t2g band narrows as the concentration of conduction electrons in the t2g band decreases. These two high-energy absorption bands fall entirely within the ultraviolet spectral region, and the absorption edge in Li 4 3Ti 5 3O4 (x = 1 3) occurs at 24,300 cm-1 (3.02 eV). A low-energy absorption band is observed in compositions with x < 1 3 and in samples of Li 4 3Ti 5 3O4 reduced in hydrogen at elevated temperatures. This band straddles the boundary between the visible and infrared spectral regions and shifts toward lower energy as the concentration of conduction electrons in the t2g band decreases. The possible origins of the band are discussed; the argument is in favor of a d-d interband transition from states in the partially filled t2g band to states in the empty σ* band. © 1984.
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spelling oxford-uuid:73b9865e-f125-4047-9e72-b687f8b04f942022-03-26T19:58:17ZA STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPYJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:73b9865e-f125-4047-9e72-b687f8b04f94EnglishSymplectic Elements at Oxford1984Harrison, MEdwards, PGoodenough, JThe room-temperature diffuse-reflectance spectra of compositions within the Li1+xTi2-xO4 spinel system (0 ≤ x ≤ 1 3) show three absorption bands in the range 4000 to 48,000 cm-1. Two high-energy absorption bands correspond to charge-transfer transitions from the oxygen-2p valence band to the titanium t2g and σ* conduction bands, where the σ* band of eg character has hybridized titanium-3d and titanium-4s parentage. The absorption band arising from promotion of electrons to the empty σ* band does not alter with composition whereas the absorption band arising from promotion of electrons to the partially filled t2g band narrows as the concentration of conduction electrons in the t2g band decreases. These two high-energy absorption bands fall entirely within the ultraviolet spectral region, and the absorption edge in Li 4 3Ti 5 3O4 (x = 1 3) occurs at 24,300 cm-1 (3.02 eV). A low-energy absorption band is observed in compositions with x < 1 3 and in samples of Li 4 3Ti 5 3O4 reduced in hydrogen at elevated temperatures. This band straddles the boundary between the visible and infrared spectral regions and shifts toward lower energy as the concentration of conduction electrons in the t2g band decreases. The possible origins of the band are discussed; the argument is in favor of a d-d interband transition from states in the partially filled t2g band to states in the empty σ* band. © 1984.
spellingShingle Harrison, M
Edwards, P
Goodenough, J
A STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPY
title A STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPY
title_full A STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPY
title_fullStr A STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPY
title_full_unstemmed A STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPY
title_short A STUDY OF THE LI1+XTI2-XO4 SPINEL SYSTEM BY DIFFUSE-REFLECTANCE SPECTROSCOPY
title_sort study of the li1 xti2 xo4 spinel system by diffuse reflectance spectroscopy
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