Circular dichroism in the angle-resolved C 1s photoemission spectra of gas-phase carvone enantiomers

Harding, Christopher John; Mikajlo, Elisabeth; Powis, Ivan; Barth, Silko; Joshi, Sanjeev; Ulrich, Volker; Hergenhahn, U.

doi:10.1063/1.2136150

Cited by 40 publications

(45 citation statements)

References 37 publications

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“…The commonly used SFA fails in describing this effect, which leads to the conclusion that not only the orbital from which ionization takes place is important, but also the final scattering state of the emitted electron. This is in accordance with findings in the single-photon PECD, where an asymmetry occurs even with an achiral initial orbital, indicating that the scattering state plays a vital role in the process [39,40]. We have demonstrated that a rather simple approximation for the scattering state is sufficient to yield a nonzero PECD effect and thus to overcome a fundamental limitation of the plain SFA.…”

Section: Discussionsupporting

confidence: 76%

Photoelectron circular dichroism of chiral molecules studied with a continuum-state-corrected strong-field approximation

Dreissigacker

Lein

2014

Phys. Rev. A

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(2013)], we investigate the origin of this effect theoretically. We show that it is not possible to describe photoelectron circular dichroism with the commonly used strong-field approximation due to its plane-wave nature. We therefore apply the Born approximation to the scattering state and use this as a continuum-state correction in the strong-field approximation. We obtain electron distributions for the molecules camphor and fenchone. In order to gain physical insight into the process, we study the contributions of individual molecular orientations.

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Section: Discussionsupporting

confidence: 76%

Photoelectron circular dichroism of chiral molecules studied with a continuum-state-corrected strong-field approximation

Dreissigacker

Lein

2014

Phys. Rev. A

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“…As such it must be very largely uninfluenced by the handedness of the molecular framework within which it is located, especially so when, as in carvone, it is localized at some distance from the asymmetric carbon centre. Nevertheless, core level PECD 4,7 has been found to be at least comparable in magnitude to typical valence shell results. 8,9,11 …”

Section: Introductionmentioning

confidence: 58%

“…7,[11][12][13] At the same time the successful application of theoretical models to treat the experimental data provides clear evidence that not just molecular conformation, but also absolute configuration could be assigned with such experimental data.…”

Section: Introductionmentioning

confidence: 94%

“…14,20 In the present work we update previous calculations made for the carvone molecule. 7,12 CMS-Xa calculations are made using model potentials that subdivide the molecule into overlapping spherical regions centred at each atomic site, the positions of these atomic centres being obtained from MP2/6-31G(p,d) optimized geometries. For the new work the atomic sphere radii have been taken from the optimized values suggested by Takai and Johnson, 21 however, the H atom radius suggested by this source leads to excessive overlap of the central carbon atom in tetrahedral geometries, and experience with CMSXa PECD calculations suggests that consequently overemphasised spatial averaging in the C atom vicinity can excessively smear the potential.…”

Section: Computational Detailsmentioning

confidence: 99%

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Photoelectron circular dichroism: Chiral asymmetry in the angular distribution of electrons emitted by (+)‐S‐carvone

Powis

2008

Chirality

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The technique of photoelectron circular dichroism (PECD) is introduced and illustrated by the presentation of results obtained for the C 1s core ionization of (+)-S-carvone enantiomers. Using circularly polarized ionizing radiation, large chiral effects in the angular distribution of photoelectrons emitted from a dilute, randomly oriented gas phase sample can be detected. This effect is predicted in the pure electric dipole approximation and is expected to be quite general. The forward-backward asymmetry regularly exceeds 10%, as demonstrated here for the carbonyl C 1s photoemission of carvone. Calculations are presented that reveal a pronounced dependence of this effect on molecular conformation. In the case of carvone the PECD associated with the C 1s electron localized at the carbonyl group varies with orientation of the isopropenyl tail group at the opposite end of the molecule. Comparisons of calculations with experiment confirm the molecular configuration and permit inferences to be drawn concerning the relative conformer populations in the experimental sample.

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“…In a sudden approximation for the ionization the emitted HOMO and SHOMO electrons (single photon case) and the Rydberg electrons (multiphoton case) will scatter off the same two ion core potentials. The importance of such final state scattering in PECD is well established, 6,37 it is after all how the photoelectron from a strongly localised, essentially achiral initial orbital senses the chirality of the molecule as it departs. On the other hand, the initial orbital enters into the dipole matrix elements and is not without influence.…”

Section: Photoelectron Circular Dichroismmentioning

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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Circular dichroism in the angle-resolved C 1s photoemission spectra of gas-phase carvone enantiomers

Cited by 40 publications

References 37 publications

Photoelectron circular dichroism of chiral molecules studied with a continuum-state-corrected strong-field approximation

Photoelectron circular dichroism of chiral molecules studied with a continuum-state-corrected strong-field approximation

Photoelectron circular dichroism: Chiral asymmetry in the angular distribution of electrons emitted by (+)‐S‐carvone

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

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