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The study experimentally investigates orbital rotation upon ionization in chiral epichlorohydrin by analyzing photoelectron dynamics in the Cl 3p Cooper minimum region using angle-resolved photoelectron spectroscopy. Observed Cooper minimum β oscillations in only two valence photoionization channels could not be explained by Hartree-Fock or DFT calculations. The authors demonstrate that incorporating electron correlation effects via equation-of-motion coupled cluster singles and doubles Dyson orbitals is necessary to accurately characterize the four lowest-lying molecular cation states and explain the observed dynamics.
Chiral molecules reveal orbital rotation upon ionization, a subtle electron correlation effect, through unexpected oscillations in photoelectron angular distributions near the Cooper minimum.
A peculiar electron correlation effect, leading to orbital rotation upon ionization, theoretically predicted long ago, was never experimentally characterized. The effect is expected to appear prominently in the photoionization of chiral molecules, due to the lack of symmetry constraints to wave-functions mixing. This is observed to have a profound effect on the photoelectron dynamics, as here demonstrated by investigating \b{eta} asymmetry parameters and partial cross-section observables in the Cl 3p Cooper minimum region of epichlorohydrin, a chiral prototype system. Angle-resolved photoelectron spectroscopy with tunable synchrotron radiation allowed measuring Cooper minimum $\beta$ oscillations, which were observed for solely two valence photoionization channels. The nature and number of channels exhibiting such dynamical behavior, along with the extent of the observed oscillation amplitudes, could not be accounted for by predictions based on Hartree-Fock (HF) and Density Functional Theory (DFT). These features could only be explained by incorporating correlation effects, which mix single-hole configurations of identical symmetry, in the characterization of the four lowest-lying molecular cation states, via equation-of-motion coupled cluster singles and doubles Dyson orbitals.
