Unexpectedly large difference of the electron density at the nucleus in the 4p ²P_1/2,3/2 fine-structure doublet of Ca^+

We measured the isotope shift in the ²S_1/2-²P_3/2 (D2) transition in singly-ionized calcium ions using photon recoil spectroscopy. The high accuracy of the technique enables us to resolve the difference between the isotope shifts of this transition to the previously measured isotopic shifts of the ²S_1/2-²P_1/2 (D1) line. This so-called splitting isotope shift is extracted and exhibits a clear signature of field shift contributions. From the data we were able to extract the small difference of the field shift coefficient and mass shifts between the two transitions with high accuracy. This J-dependence is of relativistic origin and can be used to benchmark atomic structure calculations. As a first step, we use several ab initio atomic structure calculation methods to provide more accurate values for the field shift constants and their ratio. Remarkably, the high-accuracy value for the ratio of the field shift constants extracted from the experimental data is larger than all available theoretical predictions.