Fragmentation Mechanisms for Multiply-Charged Cations
An analysis is presented of the fragmentation of multiply-charged cations AB(n+1)+ into An+ + B+ for cases in which the potential energy curve for the fragmentation can be satisfactorily described as arising from an avoided crossing between an attractive state corresponding to A(n+1)+ + B and a repulsive state corresponding to An+ + B+. An important quantity is the Gill A parameter, given by the difference in ionization energies of An+ and B. A large A corresponds to an early transition structure for the fragmentation reaction whereas a small A corresponds to a late transition structure. In the latter case, the value of A leads readily to estimates of the transition structure bond length and of the kinetic energy released during the fragmentation.
KeywordsTransition Structure Potential Energy Curve Kinetic Energy Release Adiabatic Electron Affinity Short Bond Length
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