Simultaneous, enantiomer-specific identification of chiral molecules in multi-component mixtures is extremely challenging. Many established techniques for single-component analysis fail to provide selectivity in multi-component mixtures and lack sensitivity for dilute samples. Here we show how enantiomers may be differentiated by mass-selected photoelectron circular dichroism using an electron–ion coincidence imaging spectrometer. As proof of concept, vapours containing ∼1% of two chiral monoterpene molecules, limonene and camphor, are irradiated by a circularly polarized femtosecond laser, resulting in multiphoton near-threshold ionization with little molecular fragmentation. Large chiral asymmetries (2–4%) are observed in the mass-tagged photoelectron angular distributions. These asymmetries switch sign according to the handedness (R- or S-) of the enantiomer in the mixture and scale with enantiomeric excess of a component. The results demonstrate that mass spectrometric identification of mixtures of chiral molecules and quantitative determination of enantiomeric excess can be achieved in a table-top instrument.

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.

Limonene is ionized by circularly polarized 420 nm femtosecond laser pulses. Ion mass and photoelectron energy spectra identify the dominant (2 + 1) multiphoton ionization mechanism, aided by TDDFT calculations of the Rydberg excitations. Photoelectron circular dichroism measurements on pure enantiomers reveal a chiral asymmetry of ±4 %.

Multiphoton photoelectron circular dichroism (MP-PECD) has been observed as an asymmetry in the angular distribution of photoelectrons emitted in the ionization of pure enantiomers of the small chiral molecule methyloxirane using a femtosecond laser operated at 420 nm. Energetically, this requires the uptake of four photons. By switching the laser between left- and right-circular polarization, and observing the differences in the full three-dimensional electron momentum distribution recorded in an electron-ion coincidence technique, the chiral (odd) terms in the angular distribution expression can be isolated. Electron events can additionally be filtered by coincident ion mass, providing mass-tagged electron distributions and quantitative measures of the MP-PECD asymmetry that help characterize the different ionization channels. For the production of ground state parent cation, the magnitude of the mean chiral asymmetry is measured to be 4.7%, with a peak magnitude exceeding 10%