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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 molecule's orientation and photoelectron emission direction 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., Comment: 5 figures

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., Comment: 6 figs

The absolute generalized cross sections and angular distribution parameters of photoelectrons for the two-photon above threshold $3p$-ionization of Ar were calculated in the exciting photon energy range from 15.76 to 36 eV. The correlation function technique developed earlier was extended for the case when an intermediate-state function is of a continuum-type. We show that two-photon ionization of Ar near the $3p^{4}$ threshold to a large extent is determined by the $(3p\dashrightarrow\varepsilon d)^{2}$ two-photon absorption via the giant resonance. This many-electron correlation causes (i) an increase of the photoionization cross sections by more than a factor of 3; (ii) the appearance of resonances in the exciting-photon energy range of the doubly-excited states. The predictions are supported by a good agreement between length and velocity results obtained after taking into account of the higher-order perturbation theory corrections., Comment: 11 pages, 8 figures, 26 bibliography

A detailed theoretical analysis of the 1s photoionization of neon is presented. It is found that the most significant many-electron correlation in computing photoionization of inner shells is the rearrangement of the outer shells caused by the inner vacancy. Further noticeable effects are: (i) the polarization of the ion core by the outgoing photoelectron and (ii) the coherent effect of double excitation/ionization. The core polarization increases the photoionization cross section by about 10% at the 1s threshold, and the coherent excitation results in further increases by about 5%. Incoherent excitation of the satellite channel leads to an additional 10% increase in the photoabsorption cross section in the double-ionization threshold region., Comment: 6 pages, 3 figures, 22 bibliography

X-ray as well as electron diffraction are powerful tools for structure determination of molecules. Studies on randomly oriented molecules in the gas-phase address cases in which molecular crystals cannot be generated or the interaction-free molecular structure is to be addressed. Such studies usually yield partial geometrical information, such as interatomic distances. Here, we present a complementary approach, which allows obtaining insight to the structure, handedness and even detailed geometrical features of molecules in the gas phase. Our approach combines Coulomb explosion imaging, the information that is encoded in the molecular frame diffraction pattern of core-shell photoelectrons and ab initio computations. Using a loop-like analysis scheme we are able to deduce specific molecular coordinates with sensitivity even to the handedness of chiral molecules and the positions of individual atoms, as, e.g., protons., Comment: 13 pages, 3 figures