The formation of K+center dot center dot center dot Cl heavy-Rydberg ion-pair states through dissociative electron transfer in K(np)/CCl4, n = 16-50, collisions is examined, the product ion-pair states being detected directly through electric field-induced dissociation. The results are analyzed with the aid of a Monte Carlo collision code that models both initial Rydberg electron capture and the subsequent evolution of the ion pairs. The data demonstrate the production of long-lived (tau >> 10 mu s) high-angular-momentum K+center dot center dot center dot Cl ion-pair states and suggest that Rydberg atom collisions can generate a wide variety of heavy-Rydberg species facilitating study of their physical and chemical properties. (C) 2009 Elsevier B. V. All rights reserved.