Circular dichroism in photoelectron spectroscopy of free chiral molecules: Experiment and theory on methyl-oxirane

Turchini, S.; Zema, N.; Contini, G.; Alberti, G.; Alagia, Michele; Stranges, Stefano; Fronzoni, G.; Stener, Mauro; Decleva, P.; Prosperi, T.

doi:10.1103/physreva.70.014502

Cited by 85 publications

(81 citation statements)

References 13 publications

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“…It was also noticed that PECD changes with the binding energy of a system, i.e., it is different for the ionization of different molecular orbitals [2]. Furthermore, a strong dependence of PECD on the photoelectron kinetic energy (exciting-photon energy) was found experimentally and theoretically for outer-shell photoionization of methyloxirane [7][8][9], chiral derivates of oxirane [10], as well as camphor and fenchone [11][12][13].…”

Section: Introductionmentioning

confidence: 99%

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

et al. 2017

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The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C3H3F3O, is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly-symmetric O 1s and F 1s electronic orbitals, which are localized on different molecular sites. The respective dichroic β1 and angular distribution β2 parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron radiation and velocity map imaging spectroscopy. The present experimental results are in good agreement with the outcome of ab initio electronic structure calculations. We report a sizable chiral asymmetry β1 of up to about 9% for the K-shell photoionization of oxygen atom. For the individual fluorine atoms, the present calculations predict asymmetries of similar size. However, being averaged over all fluorine atoms, it drops down to about 2%, as also observed in the present experiment. Our study demonstrates a strong emitter-and site-sensitivity of PECD in the one-photon inner-shell ionization of this chiral molecule.

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Section: Introductionmentioning

confidence: 99%

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

et al. 2017

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“…CDAD effects in randomly oriented (gas phase) chiral molecules were predicted by Ritchie 45 a few decades ago. Gas phase bromocamphor enantiomers were experimentally distinguished for the first time by Bowering et al 46 Shortly afterwards CDAD effects measured on rigid and floppy [47][48][49][50] chiral molecules demonstrate the usefulness of this methodology for highlighting the structural, conformational, and vibrational factors.…”

Section: Ir-r2pi: Conformational Landscapes Of Ground State Moleculesmentioning

confidence: 99%

Molecular and supramolecular chirality: R2PI spectroscopy as a tool for the gas‐phase recognition of chiral systems of biological interest

et al. 2008

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Dedicated to Professor Domenico Misiti on the occasion of his 75th birthday. ABSTRACTIn life sciences, diastereomeric chiral molecule/chiral receptor complexes are held together by a different combination of intermolecular forces and are therefore endowed with different stability and reactivity. Determination of these forces, which are normally affected in the condensed phase by solvent and supramolecular interactions, can be accomplished through the generation of diastereomeric complexes in the isolated state and their spectroscopic investigation. This review presents a detailed discussion of the mass resolved Resonant Two Photon Ionization (R2PI-TOF) technique in supersonic beams and introduces an overview of various other technologies currently available for the spectroscopic study of gas phase chiral molecules and supramolecular systems. It reports case studies primarily from our recent work using R2PI-TOF methodology for chiral recognition in clusters containing molecules of biological interest. The measurement of absorption spectra, ionization and fragmentation thresholds of diastereomeric clusters by this technique allow the determination of the nature of the intrinsic interactions, which control their formation and which affect their stability and reactivity.

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“…As a prototypical chiral molecule, methyloxirane's PECD has been investigated, without vibrational resolution, in both single photon VUV [28][29][30][31] and (3+1) REMPI [32] ionization schemes. We have also previously made a comparative study [31] with the analogous trifluoromethyloxirane (TFMOX) and now we continue this to examine at higher resolution the vibrationally-resolved PECD of both molecules.…”

Section: Introductionmentioning

confidence: 99%

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

et al. 2017

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Ivan (2017) Identifying and understanding strong vibronic interaction effects observed in the asymmetry of chiral molecule photoelectron angular distributions. ChemPhysChem, 18 (5 A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription. AbstractElectron-ion coincidence imaging is used to study chiral asymmetry in the angular distribution of electrons emitted from randomly-oriented enantiomers of two molecules, methyloxirane and trifluoromethyloxirane, upon ionization by circularly polarized VUV synchrotron radiation. Vibrationally-resolved photoelectron circular dichroism (PECD) measurements of the outermost orbital ionization reveal unanticipated large fluctuations in the magnitude of the forward-backward electron scattering asymmetry, including even a complete reversal of direction. Identification and assignment of the vibrational excitations is supported by Franck-Condon simulations of the photoelectron spectra. A previously proposed quasi-diatomic model for PECD is developed and extended to treat polyatomic systems. The parametric dependence of the electronic dipole matrix elements on nuclear geometry is evaluated in the adiabatic approximation, and provokes vibrational level dependent shifts in amplitude and phase, to which the chiral photoelectron angular distributions are especially sensitive. It is shown that single quantum excitation of those vibrational modes which experience only a relatively small displacement of the ion equilibrium geometry along the normal coordinate, and which are then only weakly excited in the Franck-Condon limit, can be accompanied by big shifts in scattering phase; hence the observed big fluctuations in PECD asymmetry for such modes.

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Circular dichroism in photoelectron spectroscopy of free chiral molecules: Experiment and theory on methyl-oxirane

Cited by 85 publications

References 13 publications

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

Emitter-site-selective photoelectron circular dichroism of trifluoromethyloxirane

Molecular and supramolecular chirality: R2PI spectroscopy as a tool for the gas‐phase recognition of chiral systems of biological interest

Identifying and Understanding Strong Vibronic Interaction Effects Observed in the Asymmetry of Chiral Molecule Photoelectron Angular Distributions

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