The appearance of ion-pair processes has been studied in H 2 , CO, NO and O 2 . The different thresholds successively observed for each process have been interpreted. Using the results from the convolution of theoretical models of the ionization efficiency curves and the deconvolution of their first differential, it was possible: (i) to propose a method for the determination of the threshold energy of an ion-pair process, (ii) to show that, except for H 2 , the shape of the cross-section of an ion-pair process as a function of the electron excess energy is a step-function and (iii) to determine the kinetic energy distribution of the negative ions and consequently to form an idea about the relative position of the potential energy curves of the excited states of the molecule, decaying by ion-pair process, with respect to the ground state of the molecule. Our analysis suggests that, for CO and NO, some of the observed absorption bands, labelled by Tanaka as P i , (i = 1-5), might be related to the existence of some excited states of these molecules, correlated with an ion-pair as dissociation products.