In this study, we use the relativistic multiconfiguration Dirac–Fock method (MCFD) to compute the probabilities of radiative and radiationless vacancy transfer from K- to L1-, L2-, and L3− subshells in 16S, 18Ar, 22Ti, 29Cu, 30Zn, 32Ge, 33As, 34Se, 36Kr, 40Zr, 48Cd, 50Sn, 52Te, 80Hg, 83Bi, and 86Rn atoms. Semi-theoretical calculations for elements within the atomic range of 18 ≤ Z ≤ 96 (18Ar to 96Cm) were also conducted, leveraging available data on radiative and radiationless transitions from the scientific literature. The theoretical calculation results aligned well with the values calculated semi-theoretically and with other published works. However, some notable differences were identified.