Photoelectron shake-ups as a probe of molecular symmetry: 4d XPS analysis of I3− in solution
Literature Information
Jesper Norell, Gilbert Grell, Oliver Kühn, Michael Odelius, Sergey I. Bokarev
A combination of multi-configurational restricted active space calculations with a Dyson orbital formalism has been applied for accurate simulations of 4d photo-electron spectra of the I3− molecular ion. The analysis based on the occupation numbers of natural orbitals allowed to predict and rationalize the spectral fingerprints of solvent-induced nuclear asymmetry. In particular, it demonstrates how the nuclear asymmetry directly causes an increase of shake-up intensity. The relative intensity of shake-up and main features of the I 4d XPS spectrum could therefore serve as a simplified experimental observable of structural asymmetry, complementary to changes in the shape of the main spectral features.
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