[en] The electronic structure of chromium-nickel austenite stainless steels of type Kh20N20 and Kh10N20, in particular, added with 4 to 6% Si, is studied using nuclear γ-resonance (Moessbauer) spectroscopy. The structure varies significantly depending on the chromium and silicon content. Low-chromium steels are used for the modeling of chromium-depleted boundary zones that neighbor chromium-rich excess phases. Eventually, a mechanism of the intergranular corrosion of stainless steels that takes into account the changes in the electronic structure of the chromium-depleted boundary zones is first suggested. These changes in the chemisorption interaction of the iron core ions with corrosive components of the medium, cannot but affect the zones' stability. It is this interaction that synergistically intensifies the intergranular corrosion of austenite stainless steels containing combinations of silicon dopant and carbon additions, or the phosphorus and carbon additions