It has been found that if the order of asymmetry of the quasimolecule atoms formed M=Z_H/Z_L(1.65, correlation of the molecular orbitals (MO) occurs according to the MO correlation rules of weakly asymmetric quasimolecules. The formation of vacancies in the inner electron shells of fragments produced in the fission of ²³⁵U and ²⁵²Cf nuclei are considered on the basis of the MO correlation diagrams. The probability of vacancy formation in the L shell of the light fragments and the M shell of the heavy fragments proved to be almost unity.