Subvalence 3s-shell photoionization resonances of Ca were measured with monochromatized synchrotron radiation and photoion time-of-flight spectroscopy method. Charge resolved photoion yield spectra were obtained. Broad peak structures were found in the Ca þ spectrum and shallow window structures were found in the Ca 2þ spectrum. We porformed MCDF calculations to assign the resonance structures. The 3s-shell photoionization of Ar and K were also measured for comparison. A systematic increase was observed in Fano-Beutler parameter and in the resonance width along with the increase of atomic number from Z ¼ 18(Ar) to 20(Ca). We discuss also the spectral structures that could be of the 3p double-shake-up satellites, which are observed in the 3s photoionization region.

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