Sensitivity of photoelectron circular dichroism to structure and electron dynamics in the photoionization of carvone and related chiral monocyclic terpenone enantiomers

Harding, Chris J.; Powis, Ivan
December 2006
Journal of Chemical Physics;12/21/2006, Vol. 125 Issue 23, p234306
Academic Journal
The photoelectron circular dichroism that arises in the angular distribution of photoelectrons emitted from the carbonyl group in randomly oriented pure enantiomers of carvone, and a number of carvone derivatives, is investigated by continuum multiple scattering calculations. Core ionization of carbonyl C 1s orbitals is examined for six different isopropenyl tail conformations of carvone. These show clear differences of behavior both between axial and equatorial conformations, and between the three rotational conformers of each. The pronounced dependence of the dichroism on orientation of a tail grouping, itself remote from the localized initial C 1s site, indicates the presence of long range final state photoelectron scattering effects. Analogous data for the outermost valence orbital, partially localized on the carbonyl group, are also presented. The apparently enhanced sensitivity of the dichroism exhibited in this work is discussed in terms of the particular dependence on photoelectron interference effects that is probed by the dichroism measurement and is contrasted with the usual β parameter and cross section determinations.


Related Articles

  • Valence photoionization dynamics in circular dichroism of chiral free molecules: The methyl-oxirane. Stranges, S.; Turchini, S.; Alagia, M.; Alberti, G.; Contini, G.; Decleva, P.; Fronzoni, G.; Stener, M.; Zema, N.; Prosperi, T. // Journal of Chemical Physics;6/22/2005, Vol. 122 Issue 24, p244303 

    The dynamical behavior of circular dichroism for valence photoionization processes in pure enantiomers of randomly oriented methyl-oxirane molecules has been studied by circularly polarized synchrotron radiation. Experimental results of the dichroism coefficient obtained for valence...

  • Circular dichroism in the photoelectron angular distribution from randomly oriented enantiomers of camphor. Garcia, Gustavo A.; Nahon, Laurent; Lebech, Mogens; Houver, Jean-Christophe; Dowek, Danielle; Powis, Ivan // Journal of Chemical Physics;11/1/2003, Vol. 119 Issue 17, p8781 

    Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented chiral molecules has been observed in experiments that use circularly polarized VUV synchrotron radiation. Photoionization of the outermost carbonyl oxygen lone pair electrons from pure...

  • Photoionization of the valence orbitals of OH. Stephens, J. A.; McKoy, V. // Journal of Chemical Physics;2/1/1988, Vol. 88 Issue 3, p1737 

    We report the results of studies of the photoionization cross sections and asymmetry parameters for the 3σ and 1π levels of OH, corresponding to the production of the A 3Π, c 1Π, a 1Δ, b 1Σ+, and X 3Σ- molecular ions. The calculations employed multiplet-specific...

  • (1+ 1) CDAD: A new technique for studying photofragment alignment. Dubs, Richard L.; Dixit, S. N.; McKoy, V. // Journal of Chemical Physics;5/15/1987, Vol. 86 Issue 10, p5886 

    We report a new technique for measuring photofragment alignment in the gas phase by observing circular dichroism in photoelectron angular distributions (CDAD). This technique is well suited for determining the gas phase alignment of linear molecules. The experiment involves excitation of the...

  • Photoionization of epichlorohydrin enantiomers and clusters studied with circularly polarized vacuum ultraviolet radiation. Daly, Steven; Powis, Ivan; Garcia, Gustavo A.; Soldi-Lose, Héloïse; Nahon, Laurent // Journal of Chemical Physics;2/14/2011, Vol. 134 Issue 6, p064306 

    The photoionization of enantiomerically pure epichlorohydrin (C3H5OCl) has been studied using linearly and circularly polarized vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum was recorded and the first three bands assigned using molecular orbital calculations for...

  • A table-top ultrashort light source in the extreme ultraviolet for circular dichroism experiments. Ferré, A.; Handschin, C.; Dumergue, M.; Burgy, F.; Comby, A.; Descamps, D.; Fabre, B.; Garcia, G. A.; Géneaux, R.; Merceron, L.; Mével, E.; Nahon, L.; Petit, S.; Pons, B.; Staedter, D.; Weber, S.; Ruchon, T.; Blanchet, V.; Mairesse, Y. // Nature Photonics;Feb2015, Vol. 9 Issue 2, p93 

    Circular dichroism in the extreme ultraviolet range is broadly used as a sensitive structural probe of matter, from the molecular photoionization of chiral species to the magnetic properties of solids. Extending such techniques to the dynamical regime has been a long-standing quest of...

  • Vibronic effects in magnetic vibrational circular dichroism of the triply degenerate vibration. Theoretical analysis for the ν6 vibration of tungsten hexacarbonyl. Pawlikowski, M.; Devine, T. R. // Journal of Chemical Physics;8/1/1985, Vol. 83 Issue 3, p950 

    The MVCD and infrared absorption spectra of a triply degenerate vibration are discussed in the frame of a simple molecular model applicable for molecules of cubic symmetry. The presented results show that vibronic contribution to infrared intensity can dominate or compete with ground state...

  • Vertical-type chiroptical spectrophotometer (I): Instrumentation and application to diffuse reflectance circular dichroism measurement. Harada, Takunori; Hayakawa, Hiroshi; Kuroda, Reiko // Review of Scientific Instruments;Jul2008, Vol. 79 Issue 7, p073103 

    We have designed and built a novel universal chiroptical spectrophotometer (UCS-2: J-800KCMF), which can carry out in situ chirality measurement of solid samples without any pretreatment, in the UV-vis region and with high relative efficiency. The instrument was designed to carry out...

  • Circular dichroism of angular correlation patterns in two-step and direct double photoionization. Soejima, Kouichi // AIP Conference Proceedings;2000, Vol. 500 Issue 1, p136 

    Angular correlation patterns of N[sub 5]-O[sub 23]O[sub 23] [sup 1]S[sub 0] Auger electrons in coincidence with 4d[sub 5/2] photoelectrons in two-step double photoionization of xenon and those of two emitted photoelectrons in coincidence with each other in direct double photoionization of helium...


Read the Article


Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics