Electronic Excitation Energies, Three-State Intersections, and 
Photodissociation Mechanisms of Benzaldehyde and Acetophenone

Cui, Ganglong; Lu, You; Thiel, Walter

doi:10.1016/j.cplett.2012.04.008

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Electronic Excitation Energies, Three-State Intersections, and Photodissociation Mechanisms of Benzaldehyde and Acetophenone

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Cui, Ganglong
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Lu, You
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel, Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Cui, G., Lu, Y., & Thiel, W. (2012). Electronic Excitation Energies, Three-State Intersections, and Photodissociation Mechanisms of Benzaldehyde and Acetophenone. Chemical Physics Letters, 537, 21-26. doi:10.1016/j.cplett.2012.04.008.

Cite as: https://hdl.handle.net/11858/00-001M-0000-000E-E6AC-F

Abstract

We report a theoretical study on the electronically excited states and the mechanisms of photodissociation of C6H5CHO and C6H5COCH3. For both molecules, we find an S1/T2/T1 three-state intersection region, which allows for an efficient S1 → T1 intersystem crossing via the T2 state that acts as a relay. Consequently, T1 reactions become the major radical photodissociation channels. According to the computed energy profiles, T1 photodissociation mainly yields phenyl and formyl radicals in the case of benzaldehyde, and benzoyl and methyl radicals in the case of acetophenone, with different C–C bonds being cleaved preferentially. The computational results agree well with the available experimental data.