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

✍ Scribed by Daniel Kinzel; Jesús González-Vázquez; Leticia González

Book ID: 104577169
Publisher: John Wiley and Sons
Year: 2011
Tongue: English
Weight: 557 KB
Volume: 111
Category: Article
ISSN: 0020-7608
DOI: 10.1002/qua.23026

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✦ Synopsis

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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