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Potential energy surfaces of fluorobenzene radical anions
Author(s) -
Beregovaya Irina V.,
Shchegoleva Lyudmila N.
Publication year - 2002
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.10195
Subject(s) - pseudorotation , chemistry , fluorobenzene , excited state , computational chemistry , potential energy , ab initio , benzene , ion , molecular physics , photochemistry , atomic physics , molecule , organic chemistry , physics
Ab initio ROHF/6‐31+G* and MP2/6‐31+G*//ROHF/6‐31+G* calculations were used to consider fluorination's effect on potential energy surfaces (PESs) of benzene radical anion's (RAs). The Hartree–Fock PESs of symmetrically fluorinated radical anions were found to be pseudorotation surfaces. Unlike the benzene anion PES, pseudorotation surfaces include nonplanar structures. A Möbius band may represent the pseudorotation scheme of C 6 H − 6stationary structures. Cutting the band out, we may obtain a pseudorotation scheme peculiar to C 6 F − 6 . This way of PES scheme building is also applicable to partially fluorinated RAs. A complicated structure of fluorinated anions' PES results from the avoided crossing of π states closed in energy together with the presence of a low‐lying vibronically active excited σ state. The number of stationary structures involved in pseudorotation varies in the series of anions, and may be changed at a higher level of calculations. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002