Abstract.A detailed analysis of the radiative and Auger de-excitation channels of K-shell vacancy states in Fe -Fe has been carried out. Level energies, wavelengths, A-values, Auger rates and fluorescence yields have been calculated for the lowest fine-structure levels populated by photoionization of the ground state of the parent ion. Different branching ratios, namely Kα 2 /Kα 1 , Kβ/Kα, KLM/KLL, KMM/KLL, and the total K-shell fluorescence yields, ω K , obtained in the present work have been compared with other theoretical data and solid-state measurements, finding good general agreement with the latter. The Kα 2 /Kα 1 ratio is found to be sensitive to the excitation mechanism. From these comparisons it has been possible to estimate an accuracy of ∼10% for the present transition probabilities.