Skip to content

Research at St Andrews

The ground and ionic states of cyclohepta-1,3,5-triene and their relationship to norcaradiene states. New 1H and 13C NMR spectra, and analysis of a new experimental photoelectron spectrum by ab initio methods

Research output: Contribution to journalArticlepeer-review

DOI

Open Access permissions

Open

Author(s)

Michael H. Palmer, R Alan Aitken, Marcello Coreno, Monica de Simone, Cesare Grazioli, Søren V. Hoffmann, Nykola C. Jones

School/Research organisations

Abstract

The strong inter-relationship between cyclohepta-1,3,5-triene (CHT) and norcaradiene (NCD) observed in some reactions, has been extended to include the energy surfaces for some low-lying ionic states. Whilst equilibrium structures of 2A/ symmetry containing the CHT skeleton were routinely found, the structures emerging with 2A// symmetry were found to be NCD ionic states. Surface studies, by variation of the C1 to C6 distance, showed minima for both state symmetries. Curve crossing which occurs in CS symmetry, is avoided by distortion to C1 symmetry. The CHT → NCD structural change is attributed to initial conrotatory closure of the singly occupied molecular orbital. A new synchrotron-based study of the photoelectron spectrum (PES) for CHT up to 25 eV shows little vibrational structure. We have assigned the overall PES up to 17 eV in considerable detail, using a variety of theoretical methods. The vertical ionization energy (VIE) sequence in the PES for CHT ions, is predicted to be: 12A/ < 12A// < 22A/ < 22A//. The calculated lowest ionic state, with lowest vibrational frequency 87 cm-1, leads to a high density of vibrational states. The Franck-Condon (FC) envelopes of the two lowest PES bands have been analysed. The identity of the PES spectrum, as derived from CHT rather than NCD, was demonstrated by 1H and 13C nuclear magnetic resonance (NMR) spectra of the sample; this agrees with the predicted PES spectra of CHT and NCD. The NCD predicted spectrum shows significant differences from CHT.
Close

Details

Original languageEnglish
Article number144301
Number of pages15
JournalThe Journal of Chemical Physics
Volume152
Issue number14
DOIs
Publication statusPublished - 9 Apr 2020

Discover related content
Find related publications, people, projects and more using interactive charts.

View graph of relations

Related by author

  1. Homopiperazine (hexahydro-1,4-diazepine)

    Aitken, R. A., Sonecha, D. K. & Slawin, A. M. Z., 10 Apr 2021, In: Molbank. 2021, 2, 5 p., M1200.

    Research output: Contribution to journalArticlepeer-review

  2. Five-membered Rings with Two Adjacent Heteroatoms with at least One Other Element

    Aitken, R. A. & Fotherby, F. M., 18 Jan 2021, (Accepted/In press) Chapter 4.19 in Comprehensive Heterocyclic Chemistry IV. Aitken, R. A. (ed.). Elsevier (incl. Pergamon )

    Research output: Chapter in Book/Report/Conference proceedingChapter

  3. Five-membered rings with two nonadjacent heteroatoms with at least one boron

    Aitken, R. A. & Sonecha, D. K., 18 Jan 2021, (Accepted/In press) Chapter 4.18 in Comprehensive Heterocyclic Chemistry IV. Aitken, R. A. (ed.). Elsevier (incl. Pergamon )

    Research output: Chapter in Book/Report/Conference proceedingChapter

  4. The X-ray Structures of (R)-2,2'-Dimethyl-1,1'-binaphthyl and (±)-2-Bromomethyl-2'-dibromomethyl-1,1'-binaphthyl

    Aitken, R. A., Inwood, R. & Slawin, A. M. Z., 5 Jan 2021, In: Journal of Chemical Crystallography. First Online, 8 p.

    Research output: Contribution to journalArticlepeer-review

  5. (S)-1-(Ethoxycarbonyl)ethyl (2R,5S)-2,5-Dimethyl-1,3-dioxolan-4-one-2-carboxylate

    Aitken, R. A., Haslett, O. E. & Slawin, A. M. Z., 2 Jan 2021, In: Molbank. 2021, 1, 4 p., M1178.

    Research output: Contribution to journalArticlepeer-review

Related by journal

  1. The Journal of Chemical Physics (Journal)

    Sharon Elizabeth Marie Ashbrook (Member of editorial board)

    2019 → …

    Activity: Publication peer-review and editorial work typesEditor of research journal

Related by journal

  1. High-level studies of the ionic states of norbornadiene and quadricyclane, including analysis of new experimental photoelectron spectra by configuration interaction and coupled cluster calculations

    Palmer, M. H., Coreno, M., de Simone, M., Grazioli, C., Aitken, R. A., Hoffmann, S. V., Jones, N. C. & Peureux, C., 30 Nov 2020, In: The Journal of Chemical Physics. 153, 20, 16 p., 204303.

    Research output: Contribution to journalArticlepeer-review

  2. NWChem: past, present, and future

    Aprà, E., Bylaska, E. J., de Jong, W. A., Govind, N., Kowalski, K., Straatsma, T. P., Valiev, M., van Dam, H. J. J., Alexeev, Y., Anchell, J., Anisimov, V., Aquino, F. W., Atta-Fynn, R., Autschbach, J., Bauman, N. P., Becca, J. C., Bernholdt, D. E., Bhaskaran-Nair, K., Bogatko, S., Borowski, P. & 94 others, Boschen, J., Brabec, J., Bruner, A., Cauët, E., Chen, Y., Chuev, G. N., Cramer, C. J., Daily, J., Deegan, M. J. O., Dunning, T. H., Dupuis, M., Dyall, K. G., Fann, G. I., Fischer, S. A., Fonari, A., Früchtl, H., Gagliardi, L., Garza, J., Gawande, N., Ghosh, S., Glaesemann, K., Götz, A. W., Hammond, J., Helms, V., Hermes, E. D., Hirao, K., Hirata, S., Jacquelin, M., Jensen, L., Johnson, B. G., Jónsson, H., Kendall, R. A., Klemm, M., Kobayashi, R., Konkov, V., Krishnamoorthy, S., Krishnan, M., Lin, Z., Lins, R. D., Littlefield, R. J., Logsdail, A. J., Lopata, K., Ma, W., Marenich, A. V., Martin del Campo, J., Mejia-Rodriguez, D., Moore, J. E., Mullin, J. M., Nakajima, T., Nascimento, D. R., Nichols, J. A., Nichols, P. J., Nieplocha, J., Otero-de-la-Roza, A., Palmer, B., Panyala, A., Pirojsirikul, T., Peng, B., Peverati, R., Pittner, J., Pollack, L., Richard, R. M., Sadayappan, P., Schatz, G. C., Shelton, W. A., Silverstein, D. W., Smith, D. M. A., Soares, T. A., Song, D., Swart, M., Taylor, H. L., Thomas, G. S., Tipparaju, V., Truhlar, D. G., Tsemekhman, K., Van Voorhis, T., Vázquez-Mayagoitia, Á., Verma, P., Villa, O., Vishnu, A., Vogiatzis, K. D., Wang, D., Weare, J. H., Williamson, M. J., Windus, T. L., Woliński, K., Wong, A. T., Wu, Q., Yang, C., Yu, Q., Zacharias, M., Zhang, Z., Zhao, Y. & Harrison, R. J., 11 May 2020, In: Journal of Chemical Physics. 152, 18, 184102.

    Research output: Contribution to journalArticlepeer-review

  3. Spectroscopic near-infrared photodetectors enabled by strong light-matter coupling in (6,5) single-walled carbon nanotubes

    Mischok, A., Lüttgens, J., Berger, F., Hillebrandt, S. G. H., Tenopala Carmona, F., Kwon, S., Murawski, C., Siegmund, B., Zaumseil, J. & Gather, M. C., 30 Nov 2020, In: Journal of Chemical Physics. 153, 20, 7 p., 201104 .

    Research output: Contribution to journalArticlepeer-review

  4. The vacuum ultraviolet spectrum of cyclohepta-1, 3, 5-triene: analysis of the singlet and triplet excited states by ab initio and density functional methods

    Palmer, M. H., Vrønning Hoffmann, S., Jones, N. C., Coreno, M., de Simone, M., Grazioli, C. & Aitken, R. A., 3 Aug 2020, In: The Journal of Chemical Physics. 153, 4, 14 p., 054301.

    Research output: Contribution to journalArticlepeer-review

ID: 266761591

Top