The role of πσ* states in the photochemistry of the chiral fluoroethylene derivative (4-methylcyclohexylidene)fluoromethane

Authors

  • Daniel Kinzel,

    1. Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany
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  • Jesús González-Vázquez,

    1. Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany
    Current affiliation:
    1. Departamento de Quimica Fisica I, Universidad Complutense, 28040 Madrid, Spain
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  • Leticia González

    Corresponding author
    1. Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany
    • Institut für Physikalische Chemie, Friedrich-Schiller-Universität Jena, Helmholtzweg 4, 07743 Jena, Germany
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  • In memoriam of Prof. Björn Roos, for his fundamental contributions to quantum chemistry.

Abstract

Multiconfigurational ab initio calculations of the excited states and potential energy curves of the chiral fluoroethylene derivative (4-methylcyclohexylidene)fluoromethane provide evidence that πσ* states play an important role in the abstraction of HF. We show that more than the ground and valence ππ* states are necessary to correctly describe the relaxation of the title molecule upon excitation to the bright valence ππ* state. A conical intersection between the πσ* and ππ* states has been identified at the FC geometry which makes dissociation of HF in the electronic excited state possible. This conclusion is different from all the previous studies on ethylenic systems where dissociation is postulated as a ground state reaction. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111:3394–3404, 2011

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