Enantiomeric Excess Sensitivity to Below One Percent by Using Femtosecond Photoelectron Circular Dichroism

Kästner, Alexander; Lux, Christian; Ring, Tom; Züllighoven, Stefanie; Sarpe-Tudoran, C.; Senftleben, Arne; Baumert, Thomas

doi:10.1002/cphc.201501067

Cited by 87 publications

(105 citation statements)

References 26 publications

(41 reference statements)

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“…In a more extensive study using REMPI--PECD Lux et al 52 have similarly demonstrated relative e.e. determinations with better than 1% uncertainty for fenchone mixtures spanning the full range (0-100 %).…”

Section: Fenchone Datamentioning

confidence: 85%

Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

Nahon

Nag

Garcia

et al. 2016

Phys. Chem. Chem. Phys.

122

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Ivan (2016) Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity. Physical Chemistry Chemical Physics . ISSN 1463-9084 Access from the University of Nottingham repository: http://eprints.nottingham.ac.uk/32734/1/PECD_PCCP2016_Accepted_manuscript.pdf Copyright and reuse:The Nottingham ePrints service makes this work by researchers of the University of Nottingham available open access under the following conditions. This article is made available under the University of Nottingham End User licence and may be reused according to the conditions of the licence. For more details see: http://eprints.nottingham.ac.uk/end_user_agreement.pdf 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.For more information, please contact eprints@nottingham.ac.uk This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication.Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available.You can find more information about Accepted Manuscripts in the Information for Authors.Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. Photoelectron circular dichroism (PECD) manifests itself as an intense forward/backward asymmetry in the angular distribution of photoelectrons produced from randomly--oriented enantiomers by photoionization with circularly--polarized light (CPL). As a sensitive probe of both photoionization dynamics and of the chiral molecular potential, PECD attracts much interest especially with the recent performance of related experiments with visible and VUV laser sources. Here we report, by use of quasi--perfect CPL VUV synchrotron radiation and using a double imaging photoelectron/photoion coincidence (i 2 PEPICO) spectrometer, new and very accurate values of the corresponding asymmetries on showcase chiral isomers: camphor and fenchone. These data have additionally been normalized to the absolute enantiopurity of the sample as measured by a chromatographic technique. They can therefore be used as benchmarking data for new PECD experiments, as well as for theoretical models. In particular we found, especially for the outermost orbital of both molecules, a good agreement with CMS--Xα PECD modeling over the whole VUV range. We also report a spectacular sensitivity of PECD to isomerism for slow electrons, ...

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Section: Fenchone Datamentioning

confidence: 85%

Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

Nahon

Nag

Garcia

et al. 2016

Phys. Chem. Chem. Phys.

122

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“…Such developments are now attracting considerable interest because of the possibilities for time-resolved chiral probing, and convenient lab-based analytical applications that are thereby opened up. [23][24][25] In particular, the use of resonantly enhanced multiphoton ionization (REMPI), as opposed to single VUV photon ionization, creates new opportunities for increased vibrational selectivity in PECD, as ionization then occurs out of a prepared vibrational level or wavepacket. [26] Besides permitting greater control of vibrational excitation and mode specificity, REMPI brings with it opportunities for selective isomer and/or conformer specific ionization.…”

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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“…data has reached the 1% accuracy level. 15,16 So far, little has been reported regarding the effect of laser wavelength on the measured PECD asymmetry in multiphoton excitation. Lehmann et al 8 reported multi photon-(MP-) PECD data for laser excitation at 400 and 380 nm in camphor.…”

Section: Introductionmentioning

confidence: 99%

Wavelength dependent photoelectron circular dichroism of limonene studied by femtosecond multiphoton laser ionization and electron-ion coincidence imaging

Fanood

Janssen

Powis

2016

The Journal of Chemical Physics

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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. AbstractEnantiomers of the monoterpene limonene have been investigated by (2+1) resonance enhanced multiphoton ionization and photoelectron circular dichroism employing tuneable, circularly polarized femtosecond laser pulses. Electron imaging detection provides 3D momentum measurement while electron-ion coincidence detection can be used to mass-tag individual electrons. Additional filtering, by accepting only parent ion tagged electrons, can be then used to provide discrimination against higher energy dissociative ionization mechanisms where more than three photons are absorbed to better delineate the two photon resonant, one photon ionization pathway. The promotion of different vibrational levels and, tentatively, different electronic ion core configurations in the intermediate Rydberg states can be achieved with different laser excitation wavelengths (420 nm, 412 nm, and 392 nm), in turn producing different state distributions in the resulting cations. Strong chiral asymmetries in the lab frame photoelectron angular distributions are quantified, and a comparison made with a single photon (synchrotron radiation) measurement at an equivalent photon energy.

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Enantiomeric Excess Sensitivity to Below One Percent by Using Femtosecond Photoelectron Circular Dichroism

Cited by 87 publications

References 26 publications

Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

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

Wavelength dependent photoelectron circular dichroism of limonene studied by femtosecond multiphoton laser ionization and electron-ion coincidence imaging

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