Conformational Sensitivity in Photoelectron Circular Dichroism of 3-Methylcyclopentanone

Authors

  • Dr. Stefano Turchini,

    1. Istituto di Struttura della Materia, CNR, Via Fosso del Cavaliere 100, 00133 Rome (Italy)
    Search for more papers by this author
  • Dr. Daniele Catone,

    Corresponding author
    1. Istituto di Struttura della Materia, CNR, Via Fosso del Cavaliere 100, 00133 Rome (Italy)
    • Istituto di Struttura della Materia, CNR, Via Fosso del Cavaliere 100, 00133 Rome (Italy)
    Search for more papers by this author
  • Dr. Nicola Zema,

    1. Istituto di Struttura della Materia, CNR, Via Fosso del Cavaliere 100, 00133 Rome (Italy)
    Search for more papers by this author
  • Dr. Giorgio Contini,

    1. Istituto di Struttura della Materia, CNR, Via Fosso del Cavaliere 100, 00133 Rome (Italy)
    Search for more papers by this author
  • Dr. Tommaso Prosperi,

    1. Istituto di Struttura della Materia, CNR, Via Fosso del Cavaliere 100, 00133 Rome (Italy)
    Search for more papers by this author
  • Prof. Piero Decleva,

    1. Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, Via L. Giorgieri 1, I-34127 Trieste (Italy)
    2. Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM, Unità di Trieste (Italy)
    3. DEMOCRITOS CNR-IOM National Simulation Center, Trieste (Italy)
    Search for more papers by this author
  • Prof. Mauro Stener,

    1. Dipartimento di Scienze Chimiche e Farmaceutiche, Università di Trieste, Via L. Giorgieri 1, I-34127 Trieste (Italy)
    2. Consorzio Interuniversitario Nazionale per la Scienza e Tecnologia dei Materiali, INSTM, Unità di Trieste (Italy)
    3. DEMOCRITOS CNR-IOM National Simulation Center, Trieste (Italy)
    Search for more papers by this author
  • Dr. Flaminia Rondino,

    1. ENEA, C.R. Casaccia, Via Anguillarese 301, 00123 Rome (Italy)
    Search for more papers by this author
  • Dr. Susanna Piccirillo,

    1. Dip. di Scienze e Tecnologie Chimiche, Università di Roma “Tor Vergata” via della Ricerca Scientifica, 00133 Rome (Italy)
    Search for more papers by this author
  • Dr. Kevin C. Prince ,

    1. Sincrotrone Trieste, I-34149 Basovizza Trieste (Italy)
    2. IOM-CNR, I-34149, Basovizza Trieste (Italy)
    Search for more papers by this author
  • Prof. Maurizio Speranza

    1. Dip. di Chimica e Tecnologie del Farmaco, Università di Roma “La Sapienza”, Pl. A. Moro 5, 00185, Rome (Italy)
    Search for more papers by this author

Abstract

A study of (R)-3-methylcyclopentanone [(R)-3-MCP] by photoelectron spectroscopy and photoelectron circular dichroism (PECD) is presented. The synchrotron radiation gas-phase photoelectron spectra of (R)-3-MCP were measured and are discussed on the basis of different theoretical methodologies. The experimental dichroism of (R)-3-MCP for selected deconvoluted valence states and for the carbonyl carbon 1s core state are reported and reproduced well by calculated dispersions generated by considering the contributions of two different conformers. The theoretical dichroic parameters are calculated by employing a multicentre basis set of B-spline functions and a Kohn–Sham Hamiltonian. Temperature-dependent PECD studies of the HOMO state and the carbonyl carbon 1s core level allowed the separation of the contributions of each conformer by photoelectron dichroism. This new approach clearly shows how the PECD methodology is sensitive to conformational and structural changes of unoriented (R)-3-MCP in the gas phase, opening up new perspectives in the characterisation of chiral molecular systems.

Ancillary