Theoretical investigation of some magnetic and spectroscopic properties of rare-earth ions

Arthur J Freeman, R. E. Watson

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Abstract

Investigations of some magnetic and spectroscopic properties of rare-earth ions based on approximate Hartree-Fock calculations are reported. First, a set of conventional, nonrelativistic Hartree-Fock wave functions were obtained for Ce3+, Pr3+, Nd3+, Sm3+, Eu2+, Gd3+, Dy3+, Er3+, and Yb3+; second, calculations for Ce3+ were carried out in which spin-orbit coupling was directly included in the conventional Hartree-Fock equations in order to obtain some estimate of wave-function dependence on J and the resulting effects on experimental quantities. These results are then used to discuss spin-orbit splittings, hyperfine interactions, and the determination of nuclear magnetic moments, the Slater Fk(4f,Â4f) integrals, and the crystal-field parameters, Vnm=Anm, all of which depend fairly critically on the precise form of the 4f wave functions. Comparisons are made with experiment and with the result of previous theoretical investigations which relied on either Hartree or modified hydrogenic wave functions or on semiempirical parametrizations. The usual spin-orbit formula, 1dVdr, is found not to give agreement with experiment; the reasons for this are discussed, and some evidence is described which indicates the importance of including spin-orbit exchange terms between the 4f electrons and the core. The implications of this result for efforts to relate -3 integrals to experimentally observed spin-orbit coupling parameters are discussed, as is the relation (and use) of r-3 integrals to the determination of nuclear magnetic moments. Our r-3 values agree very closely (i.e., to within 5%) with Bleaney's parametrized values, and, hence, so do our estimates for the hyperfine interactions. A sampling of estimated rare-earth nuclear magnetic moments, based on the conventional Hartree-Fock r-3 data, is given; comparison with previous estimates are made; and several causes of the uncertainty in these and all other estimates are discussed. The spectroscopic properties of these ions in a crystalline field are interpreted on the basis of the simple crystal-field theory. The rnintegrals are found to be in good agreement for n=2,Â4,ÂandÂ6 with the Elliott and Stevens parametrization formula, but the assumption of the constancy with Z of the Anm is not valid, as is shown by analysis of the available trichloride and ethyl-sulfate data. Systematic discrepancies between experimental and theoretical Fk(4f,Â4f) have been found which are similar to but greater than what has been previously observed for smaller ions. Finally, the role of spin polarization and aspherical distortions (of the closed shells and the 4f electrons) is indicated, particularly from the "unrestricted" Hartree-Fock point of view, and an estimate of the field due to polarization of the core electrons is given for all the ions. Results for smaller ions and their implications for the interpretation of observed rare-earth magnetic and spectroscopic properties are sketched.

Original languageEnglish
Pages (from-to)2058-2075
Number of pages18
JournalPhysical Review
Volume127
Issue number6
DOIs
Publication statusPublished - 1962

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rare earth elements
magnetic properties
orbits
wave functions
estimates
ions
magnetic moments
crystal field theory
electrons
polarization
sulfates
sampling
chlorides
interactions
causes

ASJC Scopus subject areas

  • Physics and Astronomy(all)

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Theoretical investigation of some magnetic and spectroscopic properties of rare-earth ions. / Freeman, Arthur J; Watson, R. E.

In: Physical Review, Vol. 127, No. 6, 1962, p. 2058-2075.

Research output: Contribution to journalArticle

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N2 - Investigations of some magnetic and spectroscopic properties of rare-earth ions based on approximate Hartree-Fock calculations are reported. First, a set of conventional, nonrelativistic Hartree-Fock wave functions were obtained for Ce3+, Pr3+, Nd3+, Sm3+, Eu2+, Gd3+, Dy3+, Er3+, and Yb3+; second, calculations for Ce3+ were carried out in which spin-orbit coupling was directly included in the conventional Hartree-Fock equations in order to obtain some estimate of wave-function dependence on J and the resulting effects on experimental quantities. These results are then used to discuss spin-orbit splittings, hyperfine interactions, and the determination of nuclear magnetic moments, the Slater Fk(4f,Â4f) integrals, and the crystal-field parameters, Vnm=Anm, all of which depend fairly critically on the precise form of the 4f wave functions. Comparisons are made with experiment and with the result of previous theoretical investigations which relied on either Hartree or modified hydrogenic wave functions or on semiempirical parametrizations. The usual spin-orbit formula, 1dVdr, is found not to give agreement with experiment; the reasons for this are discussed, and some evidence is described which indicates the importance of including spin-orbit exchange terms between the 4f electrons and the core. The implications of this result for efforts to relate -3 integrals to experimentally observed spin-orbit coupling parameters are discussed, as is the relation (and use) of r-3 integrals to the determination of nuclear magnetic moments. Our r-3 values agree very closely (i.e., to within 5%) with Bleaney's parametrized values, and, hence, so do our estimates for the hyperfine interactions. A sampling of estimated rare-earth nuclear magnetic moments, based on the conventional Hartree-Fock r-3 data, is given; comparison with previous estimates are made; and several causes of the uncertainty in these and all other estimates are discussed. The spectroscopic properties of these ions in a crystalline field are interpreted on the basis of the simple crystal-field theory. The rnintegrals are found to be in good agreement for n=2,Â4,ÂandÂ6 with the Elliott and Stevens parametrization formula, but the assumption of the constancy with Z of the Anm is not valid, as is shown by analysis of the available trichloride and ethyl-sulfate data. Systematic discrepancies between experimental and theoretical Fk(4f,Â4f) have been found which are similar to but greater than what has been previously observed for smaller ions. Finally, the role of spin polarization and aspherical distortions (of the closed shells and the 4f electrons) is indicated, particularly from the "unrestricted" Hartree-Fock point of view, and an estimate of the field due to polarization of the core electrons is given for all the ions. Results for smaller ions and their implications for the interpretation of observed rare-earth magnetic and spectroscopic properties are sketched.

AB - Investigations of some magnetic and spectroscopic properties of rare-earth ions based on approximate Hartree-Fock calculations are reported. First, a set of conventional, nonrelativistic Hartree-Fock wave functions were obtained for Ce3+, Pr3+, Nd3+, Sm3+, Eu2+, Gd3+, Dy3+, Er3+, and Yb3+; second, calculations for Ce3+ were carried out in which spin-orbit coupling was directly included in the conventional Hartree-Fock equations in order to obtain some estimate of wave-function dependence on J and the resulting effects on experimental quantities. These results are then used to discuss spin-orbit splittings, hyperfine interactions, and the determination of nuclear magnetic moments, the Slater Fk(4f,Â4f) integrals, and the crystal-field parameters, Vnm=Anm, all of which depend fairly critically on the precise form of the 4f wave functions. Comparisons are made with experiment and with the result of previous theoretical investigations which relied on either Hartree or modified hydrogenic wave functions or on semiempirical parametrizations. The usual spin-orbit formula, 1dVdr, is found not to give agreement with experiment; the reasons for this are discussed, and some evidence is described which indicates the importance of including spin-orbit exchange terms between the 4f electrons and the core. The implications of this result for efforts to relate -3 integrals to experimentally observed spin-orbit coupling parameters are discussed, as is the relation (and use) of r-3 integrals to the determination of nuclear magnetic moments. Our r-3 values agree very closely (i.e., to within 5%) with Bleaney's parametrized values, and, hence, so do our estimates for the hyperfine interactions. A sampling of estimated rare-earth nuclear magnetic moments, based on the conventional Hartree-Fock r-3 data, is given; comparison with previous estimates are made; and several causes of the uncertainty in these and all other estimates are discussed. The spectroscopic properties of these ions in a crystalline field are interpreted on the basis of the simple crystal-field theory. The rnintegrals are found to be in good agreement for n=2,Â4,ÂandÂ6 with the Elliott and Stevens parametrization formula, but the assumption of the constancy with Z of the Anm is not valid, as is shown by analysis of the available trichloride and ethyl-sulfate data. Systematic discrepancies between experimental and theoretical Fk(4f,Â4f) have been found which are similar to but greater than what has been previously observed for smaller ions. Finally, the role of spin polarization and aspherical distortions (of the closed shells and the 4f electrons) is indicated, particularly from the "unrestricted" Hartree-Fock point of view, and an estimate of the field due to polarization of the core electrons is given for all the ions. Results for smaller ions and their implications for the interpretation of observed rare-earth magnetic and spectroscopic properties are sketched.

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