title: The Interplay Between Conformation and Absolute Configuration in Chiral Electron Dynamics of Small Diols.
abstract: A competition between chiral characteristics alternatively attributable to either conformation or to absolute configuration is identified. Circular dichroism associated with photoexcitation of the outer orbital of configurational enantiomers of 1,3- and 2,3-butanediols has been examined with a focus on the large changes in electron chiral asymmetry produced by different molecular conformations. Experimental gas-phase measurements offer support for the theoretical modeling of this chiroptical effect. A surprising prediction is that a conformationally produced pseudo-enantiomerism in 1,3-butanediol generates a chiral response in the frontier electron dynamics that outweighs the influence of the permanent configurational handedness established at the asymmetrically substituted carbon. Induced conformation, and specifically induced conformational chirality, may thus be a dominating factor in chiral molecular recognition in such systems.
authors.affiliation: School of Chemistry, University Park, University of Nottingham, Nottingham, NG7 2RD, UK.|Synchrotron SOLEIL, l'Orme des Merisiers, Saint Aubin BP 48, 91192, Gif sur Yvette Cedex, France.|Institut Lumiere Matière, UMR5306, CNRS, Université Lyon 1, 69622, Villeurbanne, France.
authors.forename: Steven
authors.initials: S
authors.lastname: Daly
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint Aubin BP 48, 91192, Gif sur Yvette Cedex, France.|Institut für Kernphysik, Johann Wolfgang Goethe Universität, Max-von-Laue-Strasse 1, 60438, Frankfurt am Main, Germany.
authors.forename: Maurice
authors.initials: M
authors.lastname: Tia
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint Aubin BP 48, 91192, Gif sur Yvette Cedex, France.
authors.forename: Gustavo A
authors.identifier: 0000-0003-2915-2553
authors.initials: GA
authors.lastname: Garcia
authors.affiliation: Synchrotron SOLEIL, l'Orme des Merisiers, Saint Aubin BP 48, 91192, Gif sur Yvette Cedex, France.
authors.forename: Laurent
authors.identifier: 0000-0001-9898-5693
authors.initials: L
authors.lastname: Nahon
authors.affiliation: School of Chemistry, University Park, University of Nottingham, Nottingham, NG7 2RD, UK. ivan.powis@nottingham.ac.uk.
authors.forename: Ivan
authors.identifier: 0000-0002-7941-9079
authors.initials: I
authors.lastname: Powis
keywords: 1,3-propanediol; absolute configuration; chirality; circular dichroism