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Register a new userEmitter-site selective photoelectron circular dichroism of trifluoromethyloxirane
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The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane, C3H3F3O, is studied experimentally and theoretically. Thereby, we investigate the photoelectron circular dichroism (PECD) for nearly-symmetric O 1s and F 1s electronic orbitals, which are localized on different molecular sites. The respective dichroic $beta_{1}$ and angular distribution $beta_{2}$ parameters are measured at the photoelectron kinetic energies from 1 to 16 eV by using variably polarized synchrotron radiation and velocity map imaging spectroscopy. The present experimental results are in good agreement with the outcome of ab initio electronic structure calculations. We report a sizable chiral asymmetry $beta_{1}$ of up to about 9% for the K-shell photoionization of oxygen atom. For the individual fluorine atoms, the present calculations predict asymmetries of similar size. However, being averaged over all fluorine atoms, it drops down to about 2%, as also observed in the present experiment. Our study demonstrates a strong emitter- and site-sensitivity of PECD in the one-photon inner-shell ionization of this chiral molecule.
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The photoelectron circular dichroism (PECD) of the O 1s-photoelectrons of trifluoromethyloxirane(TFMOx) is studied experimentally and theoretically for different photoelectron kinetic energies. The experiments were performed employing circularly polarized synchrotron radiation and coincidentelectron and fragment ion detection using Cold Target Recoil Ion Momentum Spectroscopy. The corresponding calculations were performed by means of the Single Center method within the relaxed-core Hartree-Fock approximation. We concentrate on the energy dependence of the differential PECD of uniaxially oriented TFMOx molecules, which is accessible through the employed coincident detection. We also compare results for differential PECD of TFMOx to those obtained for the equivalent fragmentation channel and similar photoelectron kinetic energy of methyloxirane (MOx), studied in our previous work. Thereby, we investigate the influence of the substitution of the methyl-group by the trifluoromethyl-group at the chiral center on the molecular chiral response. Finally, the presently obtained angular distribution parameters are compared to those available in literature.
Photoelectron circular dichroism (PECD) is a highly sensitive enantiospecific spectroscopy for studying chiral molecules in the gas phase using either single-photon ionization or multiphoton ionization. In the short pulse limit investigated with femtosecond lasers, resonance-enhanced multiphoton ionization (REMPI) is rather instantaneous and typically occurs simultaneously via more than one vibrational or electronic intermediate state due to limited frequency resolution. In contrast, vibrational resolution in the REMPI spectrum can be achieved using nanosecond lasers. In this work, we follow the high-resolution approach using a tunable narrow-band nanosecond laser to measure REMPI-PECD through distinct vibrational levels in the intermediate 3s and 3p Rydberg states of fenchone. We observe the PECD to be essentially independent of the vibrational level. This behaviour of the chiral sensitivity may pave the way for enantiomer specific molecular identification in multi-component mixtures: one can specifically excite a sharp, vibrationally resolved transition of a distinct molecule to distinguish different chiral species in mixtures.
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 multiphoton 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.
We report on a joint experimental and theoretical study of photoelectron circular dichroism (PECD) in methyloxirane. By detecting O 1s-photoelectrons in coincidence with fragment ions, we deduce the molecules orientation and photoelectron emission di
rection in the laboratory frame. Thereby, we retrieve a fourfold differential PECD clearly beyond 50%. This strong chiral asymmetry is reproduced by ab initio electronic structure calculations. Providing such a pronounced contrast makes PECD of fixed-in-space chiral molecules an even more sensitive tool for chiral recognition in the gas phase.
Unravelling the main initial dynamics responsible for chiral recognition is a key stepin the understanding of many biological processes. However this challenging task requires a sensitive enantiospecic probe to investigate molecular dynamics on their natural femtosecond timescale. Here we show that, in the gas phase, the ultrafast relaxationdynamics of photoexcited chiral molecules can be tracked by recording Time-ResolvedPhotoElectron Circular Dichroism (TR-PECD) resulting from the photoionisation bya circularly polarized probe pulse. A large forward/backward asymmetry along theprobe propagation axis is observed in the photoelectron angular distribution. Its evolution with pump-probe delay reveals ultrafast dynamics that are inaccessible in theangle-integrated photoelectron spectrum nor via the usual electron emission anisotropyparameter ($beta$). PECD, which originates from the electron scattering in the chiral molecular potential, appears as a new sensitive observable for ultrafast molecular dynamicsin chiral systems.
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