Polarization of emission spectra from Ti3+-Doped oxide crystals: I. Molecular orbital theory

M. Yamaga, B. Henderson, K. P. O'Donnell

Research output: Contribution to journalArticle

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Abstract

The photoluminescence spectra of Ti3+-doped YAlO3, Y3Al5O12 and Al2O3 crystals display weak zero-phonon lines and broad vibronic side bands. The zero-phonon lines are due to the splitting of the 2T2g ground state into three Kramers' doublets by the combined effects of static axial crystal field, Jahn-Teller effect and spin-orbit interaction. A molecular orbital method is used to calculate the relative intensities and polarizations of both zero-phonon lines and broad band in terms of the mixing of odd-parity ligand wavefunctions into even-parity Ti3+ wavefunctions by odd-parity crystal fields of T1u and T2u symmetries at sites with tetragonal and trigonal symmetries. The odd-parity distortions may be static or dynamic and are of crucial relevance in determining the strength of vibronically induced transitions. In general, selection rules for optical spectra are uniquely determined by group theory. The relevance of the molecular orbit description of the d-d transitions is that it permits a physical interpretation of the strength of optical spectra in terms of the covalent charge transfer from ligand ions to central ions induced by odd-parity crystal field distortion.

LanguageEnglish
Pages122-131
Number of pages10
JournalApplied Physics B Photophysics and Laser Chemistry
Volume52
Issue number2
DOIs
Publication statusPublished - 1 Feb 1991

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molecular orbitals
parity
emission spectra
oxides
crystal field theory
polarization
crystals
optical spectrum
ligands
group theory
Jahn-Teller effect
symmetry
spin-orbit interactions
ions
charge transfer
broadband
orbits
photoluminescence
ground state

Keywords

  • emission spectra
  • photoluminescence spectra
  • crystal field distortion

Cite this

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title = "Polarization of emission spectra from Ti3+-Doped oxide crystals: I. Molecular orbital theory",
abstract = "The photoluminescence spectra of Ti3+-doped YAlO3, Y3Al5O12 and Al2O3 crystals display weak zero-phonon lines and broad vibronic side bands. The zero-phonon lines are due to the splitting of the 2T2g ground state into three Kramers' doublets by the combined effects of static axial crystal field, Jahn-Teller effect and spin-orbit interaction. A molecular orbital method is used to calculate the relative intensities and polarizations of both zero-phonon lines and broad band in terms of the mixing of odd-parity ligand wavefunctions into even-parity Ti3+ wavefunctions by odd-parity crystal fields of T1u and T2u symmetries at sites with tetragonal and trigonal symmetries. The odd-parity distortions may be static or dynamic and are of crucial relevance in determining the strength of vibronically induced transitions. In general, selection rules for optical spectra are uniquely determined by group theory. The relevance of the molecular orbit description of the d-d transitions is that it permits a physical interpretation of the strength of optical spectra in terms of the covalent charge transfer from ligand ions to central ions induced by odd-parity crystal field distortion.",
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Polarization of emission spectra from Ti3+-Doped oxide crystals : I. Molecular orbital theory. / Yamaga, M.; Henderson, B.; O'Donnell, K. P.

In: Applied Physics B Photophysics and Laser Chemistry, Vol. 52, No. 2, 01.02.1991, p. 122-131.

Research output: Contribution to journalArticle

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AB - The photoluminescence spectra of Ti3+-doped YAlO3, Y3Al5O12 and Al2O3 crystals display weak zero-phonon lines and broad vibronic side bands. The zero-phonon lines are due to the splitting of the 2T2g ground state into three Kramers' doublets by the combined effects of static axial crystal field, Jahn-Teller effect and spin-orbit interaction. A molecular orbital method is used to calculate the relative intensities and polarizations of both zero-phonon lines and broad band in terms of the mixing of odd-parity ligand wavefunctions into even-parity Ti3+ wavefunctions by odd-parity crystal fields of T1u and T2u symmetries at sites with tetragonal and trigonal symmetries. The odd-parity distortions may be static or dynamic and are of crucial relevance in determining the strength of vibronically induced transitions. In general, selection rules for optical spectra are uniquely determined by group theory. The relevance of the molecular orbit description of the d-d transitions is that it permits a physical interpretation of the strength of optical spectra in terms of the covalent charge transfer from ligand ions to central ions induced by odd-parity crystal field distortion.

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