A new technique for probing chirality via photoelectron circular dichroism

Miles, Jordan; Fernandes, Daniel L. A.; Young, Andrew; Bond, C. M. M.; Crane, Stuart W.; Ghafur, O.; Townsend, David; Sá, Jacinto; Greenwood, J. B.

doi:10.1016/j.aca.2017.06.051

Cited by 38 publications

(58 citation statements)

References 46 publications

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“…Indeed, the sign and amplitude of the odd terms driving the PECD can be used to determine e.es. if these terms are known for the enantiopure samples, as shown by several groups in the one-photon [58] and multiphoton regimes [92,93], where e.es. have been derived with a precision down to 1%.…”

Section: Overview On Pecd: Case Of Fenchone and Camphor 21 Formalismmentioning

confidence: 99%

Electron asymmetries in the photoionization of chiral molecules: possible astrophysical implications

Hadidi

Božanić

Garcia

et al. 2018

Advances in Physics: X

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Photoelectron circular dichroism (PECD) is an intense orbital-specific chiroptical effect observed as asymmetries in the angular distribution of photoelectrons produced by photoionization of randomly oriented pure enantiomers with circularly polarized light. After a broad introduction placing this effect in the context of new physical chiralsensitive methods, we review the main characteristics of PECD in terms of molecular photoionization dynamics. We stress also the analytical capabilities of PECD to retrieve enantiomeric excesses (e.es.) and to probe subtle details of the whole molecular potential, some of them exemplified by the showcase camphor and fenchone molecules. We then present the case of the amino acid alanine for which an interplay between PECD and conformer population is rationalized. Based on this study, we propose a photophysical astrophysical scenario for the origin of life's homochirality, relying upon the asymmetry of the associated recoiling alanine parent ion that could lead at the relevant Lyman-α energy to an e.e. of up to 4% in a given line of sight, which appears independent of the temperature. In an attempt to generalize this scenario to other amino acids, new data on proline showing an e.e. of 12%, of the same sign as alanine, are also presented.

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Section: Overview On Pecd: Case Of Fenchone and Camphor 21 Formalismmentioning

confidence: 99%

Electron asymmetries in the photoionization of chiral molecules: possible astrophysical implications

Hadidi

Božanić

Garcia

et al. 2018

Advances in Physics: X

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“…An example of the ion To Fs pectra recorded with DELICIOUS-3 using as upersonic beam of limonene is shown in Figure 3. The parent ion region is shown as an expanded inset where,a sw ell as the monomer (136.2 amu) as econd (137.2 amu) and third (138.2 amu) peak can be attributed to limonenem olecules possessing one or two 13 Ca tn atural abundances (11% and 1% respectively). At photon energies hn = 9.5 eV and below,t he To Fs pectra are essentially the same, showingnofragmentation, with perfectly flat baselines extending up to the parent ion region.…”

Section: Photoionizationmentioning

confidence: 99%

Intense Vibronic Modulation of the Chiral Photoelectron Angular Distribution Generated by Photoionization of Limonene Enantiomers with Circularly Polarized Synchrotron Radiation

et al. 2018

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Photoionization of the chiral monoterpene limonene has been investigated using polarized synchrotron radiation between the adiabatic ionization threshold, 8.505 and 23.5 eV. A rich vibrational structure is seen in the threshold photoelectron spectrum and is interpreted using a variety of computational methods. The corresponding photoelectron circular dichroism-measured in the photoelectron angular distribution as a forward-backward asymmetry with respect to the photon direction-was found to be strongly dependent on the vibronic structure appearing in the photoelectron spectra, with the observed asymmetry even switching direction in between the major vibrational peaks. This effect can be ultimately attributed to the sensitivity of this dichroism to small phase shifts between adjacent partial waves of the outgoing photoelectron. These observations have implications for potential applications of this chiroptical technique, where the enantioselective analysis of monoterpene components is of particular interest.

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“…[7,10] Measuring PECD has been boosted by techniques capturing the full photoelectron momentum distribution such as velocity map imaging (VMI) [11] or a recently developed stereo-electron detector. [12] Recently, single-photon PECD [13,14] highlighting in addition the relevance for astrophysical research [15] has been reviewed.Note that ionization with a single photon is independent on the temporal structure of the light. At ultra-violet up to infrared wavelengths, several photons are necessary for ionization and the temporal structure becomes very important.…”

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confidence: 99%

Observation of Photoelectron Circular Dichroism Using a Nanosecond Laser

et al. 2019

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Photoelectron circular dichroism (PECD) is a fascinating phenomenon both from a fundamental science aspect but also due to its emerging role as a highly sensitive analytic tool for chiral recognition in the gas phase. PECD has been studied with single‐photon as well as multi‐photon ionization. The latter has been investigated in the short pulse limit with femtosecond laser pulses, where ionization can be thought of as an instantaneous process. In this contribution, we demonstrate that multi‐photon PECD still can be observed when using an ultra‐violet nanosecond pulse to ionize chiral showcase fenchone molecules. Compared to femtosecond ionization, the magnitude of PECD is similar, but the lifetime of intermediate molecular states imprints itself in the photoelectron spectra. Being able to use an industrial nanosecond laser to investigate PECD furthermore reduces the technical requirements to apply PECD in analytical chemistry.

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A new technique for probing chirality via photoelectron circular dichroism

Cited by 38 publications

References 46 publications

Electron asymmetries in the photoionization of chiral molecules: possible astrophysical implications

Electron asymmetries in the photoionization of chiral molecules: possible astrophysical implications

Intense Vibronic Modulation of the Chiral Photoelectron Angular Distribution Generated by Photoionization of Limonene Enantiomers with Circularly Polarized Synchrotron Radiation

Observation of Photoelectron Circular Dichroism Using a Nanosecond Laser

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