D. Toffoli | Searcharxiv

arXiv2026

Evidence of orbital mixing upon ionization via Cooper minimum photoelectron dynamics in epichlorohydrin. Experiment and Theory

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.

physics.chem-ph↗

arXiv2007

Density Functional Theory for the Photoionization Dynamics of Uracil

Photoionization dynamics of the RNA base Uracil is studied in the framework of Density Functional Theory (DFT). The photoionization calculations take advantage of a newly developed parallel version of a multicentric approach to the calculation of the electronic continuum spectrum which uses a set of B-spline radial basis functions and a Kohn-Sham density functional hamiltonian. Both valence and core ionizations are considered. Scattering resonances in selected single-particle ionization channels are classified by the symmetry of the resonant state and the peak energy position in the photoelectron kinetic energy scale; the present results highlight once more the site specificity of core ionization processes. We further suggest that the resonant structures previously characterized in low-energy electron collision experiments are partly shifted below threshold by the photoionization processes. A critical evaluation of the theoretical results providing a guide for future experimental work on similar biosystems.

physics.chem-ph↗