Intense Vibronic Modulation of the Chiral Photoelectron Angular Distribution Generated by Photoionization of Limonene Enantiomers with Circularly Polarized Synchrotron Radiation. Issue 8 (5th March 2018)

• Record Type: Journal Article
• Authors: Rafiee Fanood, Mohammad M.; Ganjitabar, Hassan; Garcia, Gustavo A.; Nahon, Laurent; Turchini, Stefano; Powis, Ivan
• Is Part Of: Chemphyschem. Volume 19:Issue 8(2018)
• Page Start: 921
• Page End: 933
• Publication Date: 2018-03-05
• Subjects: chirality -- molecular photoionization dynamics -- photoelectron -- synchrotron radiation -- terpenes; Chemistry, Physical and theoretical -- Periodicals; 541.05
• DOI: 10.1002/cphc.201701248
• Languages: English
• ISSNs: 1439-4235

Abstract

Abstract: Photoionization of the chiral monoterpene limonene has been investigated using polarized synchrotron radiation between the adiabatic ionization threshold, 8.505 and 23.5 eV. A rich vibrational structure is seen in the threshold photoelectron spectrum and is interpreted using a variety of computational methods. The corresponding photoelectron circular dichroism—measured in the photoelectron angular distribution as a forward–backward asymmetry with respect to the photon direction—was found to be strongly dependent on the vibronic structure appearing in the photoelectron spectra, with the observed asymmetry even switching direction in between the major vibrational peaks. This effect can be ultimately attributed to the sensitivity of this dichroism to small phase shifts between adjacent partial waves of the outgoing photoelectron. These observations have implications for potential applications of this chiroptical technique, where the enantioselective analysis of monoterpene components is of particular interest. Abstract : Photoionization of limonene enantiomers by circularly polarized synchrotron light produces a forward–backward asymmetry in the photoelectron angular distribution. This asymmetry is found to strongly modulate, even reversing in direction, with vibrational excitation observed in the limonene.