Evidence of orbital mixing upon ionization via Cooper minimum photoelectron dynamics in epichlorohydrin. Experiment and theory
Abstract
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 on wave-function mixing. This is observed to have a profound effect on the photoelectron dynamics, as here demonstrated by investigating the β asymmetry parameter 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 β 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 and density functional theory. 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.
Article Details
Journal Info
The Journal of Chemical Physics
American Institute of Physics
Authors (21)
L. Schio
CNR - Istituto Officina dei Materiali (IOM), Laboratorio TASC, Area Science Park Basovizza 1 , Trieste,
M. Alagia
CNR - Istituto Officina dei Materiali (IOM), Laboratorio TASC, Area Science Park Basovizza 1 , Trieste,
T. Moitra
DTU Chemistry, Technical University of Denmark 3 , Kemitorvet 207, Kongens Lyngby 2800,
D. Toffoli
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste 5 , Trieste,
A. Ponzi
Institut Ruder Bošković 6 , Bijeniška Cesta 54, Zagreb 10000,
M. Stener
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste 5 , Trieste,
S. Coriani
DTU Chemistry, Technical University of Denmark 3 , Kemitorvet 207, Kongens Lyngby 2800,
P. Decleva
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste 5 , Trieste,
O. Rebrov
Department of Physics, University of Stockholm 7 , Stockholm,
V. Zhaunerchyk
Department of Physics, University of Gothenburg 8 , Gothenburg,
M. Larsson
S. Falcinelli
Dipartimento di Ingegneria Civile ed Ambientale, Università Degli Studi di Perugia 9 , Perugia,
A. A. Dias
Laboratory for Instrumentation, Biomedical Engineering, and Radiation Physics, Departamento de Fisica, Facultade de Ciencias e Tecnologia, Universidade NOVA de Lisboa 10 , Capacarica,
D. Catone
CNR-ISM, Area Della Ricerca di Roma Tor Vergata 11 , Via del Fosso del Cavaliere 100, Roma,
S. Turchini
CNR-ISM, Area Della Ricerca di Roma Tor Vergata 11 , Via del Fosso del Cavaliere 100, Roma,
N. Zema
CNR-ISM, Area Della Ricerca di Roma Tor Vergata 11 , Via del Fosso del Cavaliere 100, Roma,
F. Salvador
CNR-ISM, Area Della Ricerca di Roma Tor Vergata 11 , Via del Fosso del Cavaliere 100, Roma,
D. Benedetti
CNR - Istituto Officina dei Materiali (IOM), Laboratorio TASC, Area Science Park Basovizza 1 , Trieste,
D. Vivoda
Elettra-Sincrotrone Trieste, Area Science Park 12 , Basovizza, Trieste,
B. Botta
Department of Chemistry and Technologies of Drugs, Sapienza University 13 , Rome I-00183,
S. Stranges
CNR - Istituto Officina dei Materiali (IOM), Laboratorio TASC, Area Science Park Basovizza 1 , Trieste,