Electronic degeneracies in symmetric (Jahn-Teller) and nonsymmetric aliphatic radical cations: Global topology of σ-bonded molecules

Shmuel Zilberg, Yehuda Haas

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

The ground-state potential surfaces of five aliphatic radical cations are investigated using a spin-pairing model. It is shown that the ground-state surface of an n-atomic system supports several stationary points (minima and transition states, including second-order ones). In addition, there are numerous nuclear configurations at which the ground state is electronically degenerate. The electronic degeneracies due to interactions between atoms bound to the same atom are either 2-fold (conical intersections) or 3-fold degenerate but not of a higher dimension. Each 3-fold degeneracy is accompanied by an even number of conical intersections (four or two). A systematic procedure for locating all of these nuclear configurations (that are in fact 3n - 8 or 3n - 11 dimensional hypersurfaces) is described. The model allows for the qualitative determination of the structure and charge distribution of the system at all of the stationary points and electronic degeneracies. Quantum chemical calculations confirm the predictions of the model, which is used to direct and facilitate the calculations.

Original languageEnglish
Pages (from-to)1810-1820
Number of pages11
JournalJournal of the American Chemical Society
Volume125
Issue number7
DOIs
StatePublished - 15 Feb 2003
Externally publishedYes

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