Intensities of Crystal Spectra of Rare‐Earth Ions

Magnetic and electric dipole transitions between levels of the 4fx configuration perturbed by a static crystalline field are treated. The expression obtained for the pure‐electronic electric‐dipole transition probability involves matrix elements of an even‐order unit tensor between the two 4fx states involved in the transition. The contributions to the transition probability from interactions, via the crystalline field, with the nd 94fx−1, 4fx−1 nd, 4fx−1 ng configurations are shown to add linearly, in such a manner as to multiply each odd k crystal‐field parameter Ak q by a constant. If ``J mixing'' in the 4fx configuration is neglected ΔJ between the upper and lower 4fx levels is restricted to six units or less. If ``L mixing'' is neglected then ΔL is also restricted to six units or less. Application is made to the fluorescence spectra of PrCl3 and EuCl3. Many of the missing and weak transitions are explained.

[1]  J. Hope,et al.  Symmetry Properties of the Wigner 9j Symbol , 1954 .

[2]  K. Hellwege,et al.  Zeeman-Effekt und Kristallfeld des hexagonalen Europiumäthylsulfats , 1957 .

[3]  C. Gorter,et al.  On the intensities and the multipole character in the spectra of the rare earth ions , 1945 .

[4]  B. Judd An analysis of the fluorescence spectrum of europium ethyl sulphate , 1959 .

[5]  C. Ballhausen,et al.  Intensities in Inorganic Complexes , 1957 .

[6]  G. Dieke,et al.  Emission Spectra of the Doubly and Triply Ionized Rare Earths , 1961 .

[7]  S. Sugano Properties of d-Electrons in Complex Salts. Part III ---Detailed Studies of the Line Spectra--- , 1960 .

[8]  R. Satten Crystalline Field Selection Rules: The Effect of Vibration‐Electronic Interaction , 1957 .

[9]  H. Bethe,et al.  Quantum Mechanics of One- and Two-Electron Atoms , 1957 .

[10]  B. Judd The Matrix Elements of Tensor Operators for the Electronic Configurations fn , 1959 .

[11]  E. Sayre,et al.  Spectra and Quantum States of the Europic Ion in Crystals. II. Fluorescence and Absorption Spectra of Single Crystals of Europic Ethylsulfate Nonahydrate , 1956 .

[12]  J. Griffith Some investigations in the theory of open-shell ions , 1960 .

[13]  G. Shortley,et al.  The Theory of Atomic Spectra , 1935 .

[14]  J. P. Elliott,et al.  The structure of the nuclei of mass 18 and 19 , 1955, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[15]  B. Judd The matrix elements of tensor operators for configurations of three equivalent electrons , 1959, Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences.

[16]  Freeman J. Dyson,et al.  Irreducible Tensorial Sets , 1960 .

[17]  S. Pasternack Transition Probabilities of Forbidden Lines. , 1940 .