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Simple models for describing the fragmentation behavior of multiply charged cations
Author(s) -
Radom Leo,
Gill Peter M. W.,
Wong Ming Wah
Publication year - 1988
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560340861
Subject(s) - diabatic , polarizability , fragmentation (computing) , diatomic molecule , chemistry , potential energy , polarization (electrochemistry) , ionization , atomic physics , kinetic energy , dication , computational chemistry , physics , ion , molecule , quantum mechanics , adiabatic process , organic chemistry , computer science , operating system
The potential energy curve describing the fragmentation of a diatomic dication AB 2+ is considered as arising from an avoided crossing between an attractive diabatic curve (correlating with A 2+ + B) and a repulsive diabatic curve (correlating with A + + B + ). The simplest avoided‐crossing ( AC ) model neglects diabatic coupling and polarization and leads to useful predictions of the transition structure bond length ( r TS ) and the kinetic energy released ( T ) in fragmentations of dicationic systems in which the difference (Δ 1 ) between the ionization energies of A + and B is small. When Δ 1 is not small, it is necessary to include diabatic coupling and polarization in the treatment. The resultant ACDCP (avoided crossing with diabatic coupling and polarization) model provides very satisfactory estimates of r TS and T for both small and large Δ 1 . Its implementation requires only atomic ionization energy and polarizability data and comes at virtually no computational cost. Both the AC and ACDCP models are readily generalized to fragmentations of more highly charged cations.