A scenario of metal cationization in which the organic molecule combines with a neutral excited metal atom is proposed. Ionization of the nascent complex occurs via ejection of an electron during the association process. Electron structure calculations for the model systems C6H6 + Me (Me - Ag, Cu, Au) using the density functional theory give a strong argument in favor of the proposed mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.