title: Analysis of diatomic bond dissociation and formation in terms of the reaction force and the position-dependent reaction force constant.
abstract: Bond dissociation and formation in diatomic molecules are analyzed in terms of the reaction force F(R) and the reaction force constant kappa(R). These were determined for a group of 13 molecules from their extended-Rydberg potential energy functions V(R), which are of near-experimental quality. From F(R) and kappa(R) comes a two-stage description of dissociation/formation. In dissociation, the first stage involves stretching of the bond, which is opposed by an increasingly negative retarding force F(R). This reaches a minimum and then begins to weaken in the second stage, which is the transition from stretched molecule to free atoms. Bond formation begins with the reverse transition, driven by a positive F(R) which reaches a maximum for the stretched molecule and then becomes a decreasing restoring force. In the stages in which the system is a stretched molecule, kappa(R) is positive with its maximum at the equilibrium bond length; it is zero at the minimum or maximum of F(R), and negative throughout the transition stages, going through a minimum. kappa(R) <0 has been found to characterize the transition portion of a reaction. This description of dissociation/formation is reinforced by computed B3LYP and Hartree-Fock force constants at different atom separations for the singlet molecules. Hartree-Fock wave function stability assessments suggest that, for the single-bonded singlet molecules, the onset of electron unpairing in dissociation comes in the neighborhood of the F(R) minimum.
authors.affiliation: Department of Chemistry, University of New Orleans, New Orleans, LA 70148, USA.
authors.forename: Jane S
authors.initials: JS
authors.lastname: Murray
authors.forename: Alejandro
authors.initials: A
authors.lastname: Toro-Labbé
authors.forename: Tim
authors.initials: T
authors.lastname: Clark
authors.forename: Peter
authors.initials: P
authors.lastname: Politzer
mesh_terms: D000465:Algorithms; D055598:Chemical Phenomena; D003198:Computer Simulation; D007700:Kinetics; D008956:Models, Chemical; D055672:Static Electricity; D013816:Thermodynamics