Adiabatic potential energy curves of forty doublet electronic states of CF have been determined by configuration interaction calculations, over the range of internuclear distances R from 1.8 to 50.0 bohr. Rydberg states of CF converging to excited electronic states of the cation are calculated above the ground state of CF+ at short R. Rydberg-valence interactions result in a complicated pattern of avoided crossings at intermediate R, leading to predissociation of the Rydberg states as well as to a rationalization of production of ground state F(P-2(0)) + C(P-3), and F(P-2(0)) + C(D-1) fragments from the dissociative recombination of CF+ + e. (C) 2011 Elsevier B. V. All rights reserved.