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The role of πσ * states in the photochemistry of the chiral fluoroethylene derivative (4‐methylcyclohexylidene)fluoromethane
Author(s) -
Kinzel Daniel,
GonzálezVázquez Jesús,
González Leticia
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23026
Subject(s) - conical intersection , chemistry , excited state , dissociation (chemistry) , valence (chemistry) , ab initio , ground state , potential energy , photodissociation , computational chemistry , ab initio quantum chemistry methods , atomic physics , molecule , photochemistry , physics , organic chemistry
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