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The angle-resolved inner-shell photoionization of R-trifluoromethyloxirane,C3H3F3O, is studied experimentally and theoretically. Thereby, we investigatethe photoelectron circular dichroism (PECD) for nearly-symmetric O 1s and F 1selectronic orbitals, which are localized on different molecular sites. Therespective dichroic $\beta_{1}$ and angular distribution $\beta_{2}$ parametersare measured at the photoelectron kinetic energies from 1 to 16 eV by usingvariably polarized synchrotron radiation and velocity map imaging spectroscopy.The present experimental results are in good agreement with the outcome of abinitio 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 asymmetriesof similar size. However, being averaged over all fluorine atoms, it drops downto about 2%, as also observed in the present experiment. Our study demonstratesa strong emitter- and site-sensitivity of PECD in the one-photon inner-shellionization of this chiral molecule.

Emitter-site selective photoelectron circular dichroism of trifluoromethyloxirane