Electron delocalization in conjugated sulfur heterocycles probed by resonant Auger spectroscopy

To help the comprehension of the RAS phenomena, we applied multiconfigurational CASSCF functions to describe the core excited and final Auger states. Using this approach, we obtained accurate transition and Auger kinetic energies, which enables the assignment of the unexpected shift between the core excitation to the low-lying π* and σ* orbitals. Additionally, to express the RAS spectroscopy in terms of chemical concepts, we applied the Natural Bond Orbitals analysis, using the stabilization energy of these orbitals to rationalize the excited states’ behavior.

Martins, J. B., de Moura, C. E. V., Goldsztejn, G., Travnikova, O., Guillemin, R., Ismail, I., Journel, L., Koulentianos, D., Barbatti, M., Lago, A. F., Céolin, D., Rocco, M. L. M., Püttner, R., Piancastelli, M. N., Simon, M., Marchenko, T. (2022) Electron Delocalisation in Conjugated Sulfur Heterocycles Probed by Resonant Auger Spectroscopy, Physical Chemistry Chemical Physics, 24 (14), 8477–8487. [Link]

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