PNNL

Abstract

Isotope shifts and hyperfine structure have been measured in 4snp 1P1 and 4snf F Rydberg states for all stable calcium isotopes and the radioisotope 41Ca using high-resolution laser spectroscopy. Triple-resonance excitation via 4s2 1S0 --- 4s4p 1P1 --- 4s4d 1D2 --- Rydberg State was followed by photoionization with a CO2 laser and mass selective ion detection. Isotope shifts for the even-mass isotopes have been analyzed to derive specific mass shift and field shift factors. The apparent isotope shifts for 41Ca and 43Ca exhibit anomalous values that are n-dependent. This is interpreted in terms of hyperfine-induced fine structure mixing, which becomes very pronounced when singlet-triplet fine structure splitting is comparable to the hyperfine interaction energy. Measurements of fine structure splittings for the predominant isotope 40Ca have been used as input parameters for theoretical calculation of the perturbed hyperfine structure. Results obtained by diagonalizing the second-order hyperfine interaction matrices agree very well with experimentally observed spectra.