TY - JOUR
T1 - Electronic degeneracies in symmetric (Jahn-Teller) and nonsymmetric aliphatic radical cations
T2 - Global topology of σ-bonded molecules
AU - Zilberg, Shmuel
AU - Haas, Yehuda
N1 - Funding Information:
Received May 15, 2006; revised July 10, 2006 *Corresponding author. Tel: +86-29-88302808; E-mail: [email protected] This work was supported by the Key Laboratory Research Plan of Education Department in Shaanxi Province of China (No. 02JS10, 05JS62).
PY - 2003/2/15
Y1 - 2003/2/15
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0037442668&partnerID=8YFLogxK
U2 - 10.1021/ja028820u
DO - 10.1021/ja028820u
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C2 - 12580607
AN - SCOPUS:0037442668
SN - 0002-7863
VL - 125
SP - 1810
EP - 1820
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 7
ER -