Photoelectron circular dichroism spectroscopy in an orbitally congested system: the terpene endoborneol.

We have measured the photoelectron circular dichroism (PECD) of single enantiomers of endoborneol in the photon region from 9.9 to 23.6 eV by combining circularly polarized synchrotron radiation and a velocity map imaging technique. A photoelectron spectrum and the state-selected fragmentation curves of this terpene were also recorded. Unlike previous case studies, the broad featureless transitions encountered here preclude an orbital by orbital analysis of the PECD, although semiquantitative features of the highest-occupied molecular orbital PECD are identified and compared to full calculations. Despite our inability to further identify individual orbitals experimentally, we show that we are able to unambiguously assign the absolute configuration by comparison with realistic simulated PECD spectra. Furthermore, the calculations predict that for electron kinetic energies above 5 eV; the contributions of individual conformers to the PECD are nearly identical. Should this observation apply to bigger biological systems, the analysis could be greatly simplified by recording high kinetic energy electrons. On the other hand the contributions of the different conformers to the slow electron PECD seem to vary more significantly, and we deduce, within the theoretical limitations, a plausible 1:1:1 distribution of the three identified conformers.