We report an experimental investigation of homochiral cluster formation in seeded molecular beam expansions of (2R,3R)-butanediol. Synchrotron radiation vacuum ultraviolet photoionization measurements have been performed using a double imaging electron-ion spectrometer in various configurations and modes of operation. These include measurements of the cluster ion mass spectra, wavelength scanned ion yields, and threshold electron spectra.
View Article and Find Full Text PDFMost large molecules are chiral in their structure: they exist as two enantiomers, which are mirror images of each other. Whereas the rovibronic sublevels of two enantiomers are almost identical (neglecting a minuscular effect of the weak interaction), it turns out that the photoelectric effect is sensitive to the absolute configuration of the ionized enantiomer. Indeed, photoionization of randomly oriented enantiomers by left or right circularly polarized light results in a slightly different electron flux parallel or antiparallel with respect to the photon propagation direction-an effect termed photoelectron circular dichroism (PECD).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2016
The valence shell photoionization of the simplest proteinaceous chiral amino acid, alanine, is investigated over the vacuum ultraviolet region from its ionization threshold up to 18 eV. Tunable and variable polarization synchrotron radiation was coupled to a double imaging photoelectron/photoion coincidence (i(2)PEPICO) spectrometer to produce mass-selected threshold photoelectron spectra and derive the state-selected fragmentation channels. The photoelectron circular dichroism (PECD), an orbital-sensitive, conformer-dependent chiroptical effect, was also recorded at various photon energies and compared to continuum multiple scattering calculations.
View Article and Find Full Text PDFA detailed study of the valence photoionization of small homochiral glycidol (C3O2H6) clusters is carried out with the help of circularly-polarized VUV synchrotron radiation by recording photoionization-based spectroscopic data detected by velocity map electron imaging with coincidence ion selection. We show that information on the stability of cationic as well as neutral chiral clusters can be obtained with enhanced sensitivity by examining the chiral fingerprint encapsulated in Photoelectron Circular Dichroism (PECD) spectra. In particular, by varying the clustering conditions we demonstrate that the PECD signal effectively carries the signature of the neutral precursor species, prior to any fragmentation of the ion, as may be inferred from the below-threshold monomer measurements (including ion imaging).
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