The local reactivity proclivities in a series of simple substituted nitrenes (N-X) and phosphinidenes (P-X) have been explored for the lowest-lying singlet and triplet electronic states within the framework of spin-polarized density functional theory (SP-DFT). Linear correlations have been found between both the global and local philicities for spin polarization and the vertical singlet-triplet energy gaps. The accumulation and depletion of the electron or spin density can be directly related to the electronegativity of the substituent atoms. The local analysis has been achieved on the basis of a recent implementation of condensed-to-site SP-DFT Fukui functions. (C) 2007 Elsevier B.V. All rights reserved.