Spin-unrestricted Kohn-Sham (KS) solutions are constructed from accurate ab initio spin densities for the prototype doublet molecules NO2, ClO2, and NF2 with the iterative local updating procedure of van Leeuwen and Baerends (LB). A qualitative justification of the LB procedure is given with a "strong" form of the Hohenberg-Kohn theorem. The calculated energies epsilon(isigma) of the occupied KS spin orbitals provide numerical support to the analogue of Koopmans' theorem in spin-density functional theory. In particular, the energies-epsilon(ibeta) of the minor spin (beta) valence orbitals of the considered doublet molecules correspond fairly well to the experimental vertical ionization potentials (VIPs) I-i(1) to the triplet cationic states. The energy-epsilon(Halpha) of the highest occupied (spin-unpaired) alpha orbital is equal to the first VIP I-H(0) to the singlet cationic state. In turn, the energies -epsilon(ia) of the major spin (alpha) valence orbitals of the closed subshells correspond to a fifty-fifty average of the experimental VIPs I-i(1) and I-i(0) to the triplet and singlet states. For the Li atom we find that the exact spin densities are represented by a spin-polarized Kohn-Sham system which is not in its ground state, i.e., the orbital energy of the lowest unoccupied beta spin orbital is lower than that of the highest occupied a spin orbital ("a hole below the Fermi level"). The addition of a magnetic field in the - z direction will shift the beta levels up so as to restore the Aufbau principle. This is an example of the nominiqueness of the mapping of the spin density on the KS spin-dependent potentials discussed recently in the literature. The KS potentials may no longer go to zero at infinity, and it is in general the differences v(ssigma)(infinity)-epsilon(isigma) that can be interpreted as (averages of) ionization energies. In total, the present results suggest the spin-unrestricted KS theory as a natural one-electron independent-particle model for interpretation and assignment of the experimental photoelectron spectra of open-shell molecules. (C) 2004 American Institute of Physics.