Except for the case of van der Waals interactions, homopolar bonds are covalent and therefore a concentration of the electron density is expected at the bond midpoint. Many experimental and theoretical studies have reported standard deformation density maps and molecular density minus spherical atoms densities, which show a depletion of electron density between formally covalently bonded atoms. For example, electron deficits are found in the theoretical map of the F-F bond in F 2 , in the experimental map of the N-N bond in carbonohydrazide, and in the experimental and theoretical maps of the O-O bond in 1,2,7,8-tetraaza-4,5,10,11-tetraoxatricyclo[6.4.1.1]tetradecane. Other partitioning schemes, such as subtraction of valence state atoms rather than spherical atoms from the total density, have been proposed to interpret these unexpected features. In the present work we examine these electronically depleted covalent bonds on the basis of the topological analysis of the electron localization function (ELF) of theoretically calculated electron densities. The attractors of ELF determine basins that are either core or valence basins. The valence basins are characterized by the number of core basins with which they share a common boundary, and this number is called the synaptic order. Disynaptic valence basins have been found for the F-F bond in F 2 , for the N-N bond in carbonohydrazide and for the O-O bond in 1,2,7,8-tetraaza-4,5,10,11tetraoxatricyclo[6.4.1.1]tetradecane. In the case of F 2 , polarization functions increase the V(F, F ) basin population, whereas accounting for the Coulomb correlation lowers this basin population. The results calculated for F 2 are compared with those obtained for other diatomic molecules, such as N 2 and O 2 , and the ELF picture of the bond compared with the molecular orbital analysis. In the case of carbonohydrazyde, the V(N, N ) basin population is the lowest among all the populations of the disynaptic valence basins present in the molecule, in good agreement with the experimental observations. Analogous results are