Electron-Withdrawing Effects in the Photodissociation of CH<sub>2</sub>ICl To Form CH<sub>2</sub>Cl Radical, Simultaneously Viewed Through the Carbon K and Chlorine L<sub>2,3</sub> X‑ray Edges
2018-09-24T00:00:00Z (GMT) by
A fundamental chlorine-containing radical, CH<sub>2</sub>Cl, is generated by the ultrafast photodissociation of CH<sub>2</sub>ICl at 266 nm and studied at both the carbon K edge (∼284 eV) and chlorine L<sub>2,3</sub> edge (∼200 eV) by femtosecond X-ray transient absorption spectroscopy. The electronic structure of CH<sub>2</sub>Cl radical is characterized by a prominent new carbon 1s X-ray absorption feature at lower energy, resulting from a transition to the half-filled frontier carbon 2p orbital (singly occupied molecular orbital of the radical; SOMO). Shifts of other core-to-valence absorption features upon photodissociation of CH<sub>2</sub>ICl to yield ·CH<sub>2</sub>Cl indicate changes in the energies of core-level transitions of carbon and chlorine to the σ*(C–Cl) valence orbital. When the C–I bond breaks, loss of the electron-withdrawing iodine atom donates electron density back to carbon and shields the carbon 1s core level, resulting in a ∼0.8 eV red shift of the carbon 1s to σ*(C–Cl) transition. Meanwhile, the 2p inner shell of the chlorine atom in the radical is less impacted by the iodine atom removal, as demonstrated by the observation of a ∼0.6 eV blue shift of the transitions at the chlorine L<sub>2,3</sub> edges, mainly due to the stronger C–Cl bond and the increased energy of the σ*(C–Cl) orbital. The results suggest that the shift in the carbon 1s orbital is greater than the shift in the σ*(C–Cl) orbital upon going from the closed-shell molecule to the radical. Ab initio calculations using the equation of motion coupled-cluster theory establish rigorous assignment and positions of the X-ray spectral features in the parent molecule and the location of the SOMO in the CH<sub>2</sub>Cl radical.