title: Conformational sensitivity in photoelectron circular dichroism of 3-methylcyclopentanone.
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.
authors.affiliation: Istituto di Struttura della Materia, CNR, Via Fosso del Cavaliere 100, 00133 Rome, Italy.
authors.forename: Stefano
authors.initials: S
authors.lastname: Turchini
authors.forename: Daniele
authors.initials: D
authors.lastname: Catone
authors.forename: Nicola
authors.initials: N
authors.lastname: Zema
authors.forename: Giorgio
authors.initials: G
authors.lastname: Contini
authors.forename: Tommaso
authors.initials: T
authors.lastname: Prosperi
authors.forename: Piero
authors.initials: P
authors.lastname: Decleva
authors.forename: Mauro
authors.initials: M
authors.lastname: Stener
authors.forename: Flaminia
authors.initials: F
authors.lastname: Rondino
authors.forename: Susanna
authors.initials: S
authors.lastname: Piccirillo
authors.forename: Kevin C
authors.initials: KC
authors.lastname: Prince
authors.forename: Maurizio
authors.initials: M
authors.lastname: Speranza
mesh_terms: D002942:Circular Dichroism; D003517:Cyclopentanes / Q000737:chemistry*; D008968:Molecular Conformation; D056951:Photoelectron Spectroscopy; D011789:Quantum Theory; D013237:Stereoisomerism; D013696:Temperature
chemical_list: C521405:3-methylcyclopentanone; D003517:Cyclopentanes