A global picture of the S₁/S₀ conical intersection seam of benzene

A global picture of the S₁/S₀ intersection seam of benzene is presented. Eleven new conical intersection critical points were located at the CASSCF level, the connectivity was mapped and the energies refined with CASPT 2. There are two seam branches related with pairs of degenerate A _{1 g} /B _{2 u} and E_g states at D _{6 h} symmetry, respectively, and the two branches are connected by a seam segment of C_s symmetry. The global energy minimum of the seam is the half-boat shaped intersection that leads to a pre-fulvenic intermediate [I.J. Palmer, I.N. Ragazos, F. Bernardi, M. Olivucci, M.A. Robb, J. Am. Chem. Soc. 115 (1993) 673]. Several other intersections that can lead to the same intermediate or vibrationally hot benzene lie in a range of 3.7 eV above the global seam minimum. There is a recurrent connectivity pattern where permutationally isomeric seam segments are connected by intersections of a higher symmetry point group. © 2010 Elsevier B.V. All rights reserved.