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Photochemistry of CF3Cl: Quenching of Charged Fragments Is Caused by Nonadiabatic Effects

Abstract : For the first time, high-level multireference electronic structure calculations have been performed to study the photochemistry of CF3Cl, allowing a comprehensive interpretation and assignment of experimental data concerning fluorescence, ion-pair formation, and generation of CF3 fragments in several electronic states. All studied dissociation channels correlate either with Cl or Cl  in the ground state. On the other hand, CF3 fragment can be generated either in the ground or excited state. A rationalization for the nonadiabatic relaxation of CF3Cl, including the formation of an (n4s) stable state and internal conversion at multiple-state intersections, has been provided. Our results explain the anomalous quenching of charged fragment after low-energy excitation experimentally observed by separate groups. We show that the CF3 +… Cl  ion pair undergoes an internal conversion to the ground state, producing neutral CF3 and Cl fragments. The results also allow understanding why CF3Cl is usually a non-emitting species and how UV emission could be induced. de Medeiros et al., Photochemistry of CF3Cl (2018) 2
Keywords : CF3CI Photochemistry
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Vanessa de Medeiros, Railton de Andrade, Gessenildo P. Rodrigues, Glauco Bauerfeldt, Elizete Ventura, et al.. Photochemistry of CF3Cl: Quenching of Charged Fragments Is Caused by Nonadiabatic Effects. Journal of Chemical Theory and Computation, American Chemical Society, 2018, 14 (9), pp.4844-4855. ⟨10.1021/acs.jctc.8b00457⟩. ⟨hal-01965454⟩

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