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The vacancy transfer probabilities of K to L1, L2 and L3 shell were measured with a new method. The L X-ray yields of targets excited by 59.5 keV incident photons, i.e., above the K edge of elements, were detected with a high-resolution Si(Li) detector. For comparison with the experimental results, theoretical calculations were made using data available on radiative and radiationless transitions. The radiative transition values of these elements were taken from the relativistic Hartree-Slater model, those of the radiationless transitions from the Dirac-Hartree-Slater model. The measured values were found to be in good agreement with theoretical ones. The hKLi (i = 1, 2, 3) values were calculated by measuring the L1x, L2x and L3x X-ray production cross-sections.