Van der Lugt-Oosterhoff model

Figure 6.13. Pericyclic funnel region of ethylene dimerization, showing two equivalent conical intersections corresponding to 1,3 and 2,4 diagonal interactions and the transition slate region at rectangular geometry (a = 0). The curves shown for a = 0 correspond to the van der Lugt-Oosterhoff model (by permission from Klessinger, 1995),...

Fig. 2. The relationship between (a) the Van der Lugt-Oosterhoff model and (b) a model (see Sec. 2.1) based on MEP computations for the photochemical electrocycliza-tion of buta-1,3-diene. The Van der Lugt-Oosterhoff model is based on an assumed (interpolated) reaction coordinate and suggests that the photochemical funnel corresponds to an avoided crossing at M (see dashed frame). MEP computations yield a different, but unbiased coordinate, corresponding to the steepest-descent path from the excited-state reactant. The reaction coordinate characterizing such a path leads to a conical intersection between the excited (5i) and ground (So) states. The framed region in part (b) indicates the position of the Van der Lugt-Oosterhoff avoided crossing in the conical intersection region.

Nenov A, KoUe P, Robb MA, de Vivie-Riedle R (2009) Beyond the van der Lugt/Oosterhoff model when the conical intersection seam and the Si minimum energy path do not cross. J Org Chem 75 123... 

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See also in sourсe #XX -- [ ]

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