Description of carbo-oxocarbons and assessment of exchange-correlation functionals for the DFT description of carbo-mers.
Mono- and polycyclic valence isomers of carbo-[3]oxocarbon C(9)O(3) and carbo-[5]oxocarbon C(15)O(5) have been characterized on the singlet spin state potential energy surface. By contrast to their geometry, their relative stability is highly sensitive to the calculation level. The performance of LDA, GGA, meta-GGA, and hybrid functionals is compared to that of HF, post-HF, and multiconfigurational calculations. The results obtained for C(9)O(3) are compared to those obtained for hydrocarbon analogues such as &[3]pericyclyne C9(H2)3 and carbo-[3]radialene C9(CH2)3 and are analyzed on the basis of an energy decomposition scheme. The respective role of the exchange and correlation counterparts of the functional in the discrepancy of the results is discussed.
Lepetit
Christine
C
Laboratoire de Chimie de Coordination, UPR 8241 CNRS, 205 Route de Narbonne, 31 077 Toulouse Cedex 4, France.
Chermette
Henry
H
Gicquel
Mickaël
M
Heully
Jean-Louis
JL
Chauvin
Remi
R