Abstract
This paper discusses the polarization of vibronically-broadened absorption and emission spectra of Cr3+ ions in ionic crystals such as MgO, CaO, YAlO3 and Gd3Sc2Ga3O12. A molecular orbital theory is presented of the selection rules of the vibronic 4T2→4A2 emission, a transition of importance in tunable laser action of the Cr3+ ion in ionic host lattices. The selection rules of optical spectroscopy are normally determined using group theoretical methods. However, the molecular orbital approach adds to the group theoretical results an identification of the contributions to the strength of vibronic sideband transitions by covalent admixtures of ligand orbitals into ground and excited states wave functions of the optical centre. In particular molecular orbital theory is used to calculate the strengths of linearly and circularly polarized components of absorption and emission spectra in the absence or presence of a static magnetic field. The theoretical results are compared with experiments and used to discuss the relative contributions to the sideband by odd-parity distortions of T1u and T2u symmetry.
Original language | English |
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Pages (from-to) | 397-418 |
Number of pages | 22 |
Journal | Journal of Luminescence |
Volume | 46 |
Issue number | 6 |
DOIs | |
Publication status | Published - 31 Jul 1990 |
Funding
The authors are indebted jointly to the SERC and British Telecom Research Laboratories for their support (Cooperative Research Grant GRD/62670) of the experimental programme of which this work forms a part. M.Y. is indebted to the SERC (GR/D/75557) for his appointment as a senior Visiting Fellow at Strathclyde University during 1986—87 and the sunimer of 1989.
Keywords
- ionic crystals
- absorption
- molecular orbital theory