Abstract
A deviation from the spin sum rule, which relates the integrated intensity of the X-ray magnetic circular dichroism (MCD) signal to the expectation value of the spin operator S z (< S z >), is numerically calculated in the case of the 3 d →4 f absorption for rare earths from the trivalent Ce to Tm. The calculation on the basis of an atomic model including the full multiplet shows that the deviation increases from ∼60 % for Ce with increasing 4 f electron number, reaches at ∼230 % for Sm and drops to less than ∼10 % for Gd and heavier rare earths. An interplay of the 3 d -4 f exchange interaction, the 3 d core spin-orbit interaction and the 4 f electron configuration in the initial ground state is shown to cause the chemical trend of the deviation from the sum rule.
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