The Role of pi sigma* States in the Photochemistry of the Chiral Fluoroethylene Derivative (4-methylcyclohexylidene)fluoromethane

作者：Kinzel Daniel; Gonzalez Vazquez Jesus; Gonzalez Leticia^*

来源：International Journal of Quantum Chemistry, 2011, 111(13): 3394-3404.

DOI：10.1002/qua.23026

• photochemistry
• excited states
• conical intersections
• photodissociation

Multiconfigurational ab initio calculations of the excited states and potential energy curves of the chiral fluoroethylene derivative (4-methylcyclohexylidene)fluoromethane provide evidence that pi sigma* states play an important role in the abstraction of HF. We show that more than the ground and valence pi pi* states are necessary to correctly describe the relaxation of the title molecule upon excitation to the bright valence pi pi* state. A conical intersection between the pi sigma* and pi pi* 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.

• 出版日期2011-11-5