A new contribution to spin-forbidden rare earth optical transition intensities: Gd3+ and Eu3

• Published in: The Journal of chemical physics 1988-08, Vol.89 (4), p.1787-1797
• Main Authors: DOWNER, M. C, BURDICK, G. W, SARDAR, D. K
• Format: Article
• Language: English
• Subjects: Condensed matter: electronic structure, electrical, magnetic, and optical properties; Electron states; Exact sciences and technology; Level splitting and interactions; Physics; Spin-orbit coupling, zeeman, stark, and strain splitting, jahn-teller effect
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.455125

Quantitative calculations show that numerous spin-forbidden linear optical transitions observed in trivalent rare earth ions acquire a major fraction of their intensity from hitherto neglected contributions involving spin–orbit linkages within excited configurations. Motivated by the importance of analogous linkages previously demonstrated in two-photon absorption, we derive a general expression applicable for all lN→lN transitions which can be incorporated into a revised Judd–Ofelt analysis of observed intensities. Presenting this revised analysis of observed linear absorption intensities for Gd3+ and Eu3+, we show that the new contribution is often comparable to standard contributions. With substantial modification of previously fitted phenomenological parameters, an improved fit to observed intensities is achieved, suggesting that reanalysis of linear intensity data for all trivalent rare earths is warranted.