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

Quansong Li, David Mendive-Tapia, Martin J. Paterson, Annapaola Migani, Michael J. Bearpark, Michael A. Robb, Lluís Blancafort

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39 Citations (Scopus)

Abstract

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 Eg states at D 6 h symmetry, respectively, and the two branches are connected by a seam segment of Cs 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.

Original languageEnglish
Pages (from-to)60-65
Number of pages6
JournalChemical Physics
Volume377
Issue number1-3
DOIs
Publication statusPublished - 25 Nov 2010

Keywords

  • Benzene
  • Conical intersection seams
  • Permutational symmetry

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