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Søren Vrønning Hoffmann

The ionic states of cyclooctatetraene. Analysis of a new experimental photoelectron spectrum by ab initio and density functional methods

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  • Michael H. Palmer, Univ Edinburgh, University of Edinburgh, Sch Chem, United Kingdom
  • Marcello Coreno, CNR, Istituto di Struttura della Materia (ISM-CNR), Consiglio Nazionale delle Ricerche (CNR), ISM, LD2 Unit, Italy
  • Monica De Simone, CNR, Consiglio Nazionale delle Ricerche (CNR), Istituto Officina dei Materiali (IOM-CNR), Lab TASC, IOM, Italy
  • Cesare Grazioli, IOM-CNR Laboratorio TASC, Italy
  • Søren Vrønning Hoffmann
  • Nykola C. Jones

A synchrotron-based study of the photoelectron spectrum (PES) for cyclooctatetraene (COT) is reported, and this has been subjected to theoretical analysis in unprecedented detail. Weak vibrational structure was observed on the lowest ionization energy (IE 1 ), but the peaks generally show very broad features. Multiconfiguration self-consistent field study confirms that the adiabatic IE (AIE) sequence is 1 2 A 1 < 1 2 B 1 < 2 2 A 1 < 1 2 A 2 < 2 2 B 1 < 3 2 A 1 . The Tamm-Dancoff approximation gives an acceptable interpretation of the PES below 20 eV. Vibrational analysis of the PES bands by Franck-Condon methods predicts well-defined vibrational structure for these ionic states. The principal contributors to the PES envelopes are the a 1 modes, and only a few are responsible for the overall shape of most bands. The high density of vibrational states, together with the known D 2d D 2d interconversion process, where the C=C and C-C bonds interchange, is attributed to the lack of the observed structure. The transition state (TS) structures for the interconversion above of several ionic states of COT have been elucidated. The intrinsic reaction coordinate procedure gave a planar TS for the X 1 A 1 (D 2d ) 1 A 1g (D 4h ) X 1 A 1 (D 2d ) process; this shows alternating C-C (1.4791 Å), C=C (1.3261 Å), and C-H (1.0780 Å) bond lengths. The planar TS is a very shallow maximum, with energy varying with the method used, Hartree-Fock 0.575 eV and second order Møller-Plesset 0.653 eV. A polynomial containing quadratic, quartic, and sextic terms gives an effectively exact fit to the surface. The lowest ionic state of COT (X 2 A 1 ) shows a similar TS for the process X 2 A 1 (D 2d ) 2 B 2u (D 4h ). This structure has alternating C-C (1.4366 Å), C=C (1.3572 Å), and C-H (1.0756 Å) bonds.

Original languageEnglish
Article number194305
JournalThe Journal of Chemical Physics
Volume150
Issue19
Number of pages10
ISSN0021-9606
DOIs
Publication statusPublished - 2019

    Research areas

  • APPROXIMATION, ATOMS, BASIS-SETS, BOND SHIFT KINETICS, NMR, VALENCE

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