Assessment of several hybrid DFT functionals for the evaluation of bond length alternation of increasingly long oligomers.
We have optimized the ground-state geometry of nine series of increasingly long oligomers, using six hybrid density functionals (O3LYP, B3LYP, B97-1, B98, PBE0, and BHHLYP) combined with three different atomic basis sets. In each case, the obtained bond length alternation (BLA) is compared to the corresponding MP2 values. Three phenomenological categories have been set up. In the first, the BLA exponentially decreases, in which case all the tested functionals give results in very good agreement with MP2. In the second category fall the symmetric oligomers that, due to the Peierls theorem, show large BLA. For these chains, BHHLYP tends to give too large and quickly converging BLA wrt chain length, while O3LYP often leads to the opposite misjudgments, and the remaining hybrids provide valuable results. In the third category, one finds asymmetric compounds presenting significantly unequal bond lengths, for which the divergence between DFT and wave function approaches can be dramatic. Indeed, all hybrids yield too small BLA values, especially for long chain lengths. We also study the effect of chain conformation on the BLA.
Jacquemin
Denis
D
Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, Namur, Belgium. denis.jacquemin@fundp.ac.be
Femenias
Antoine
A
Chermette
Henry
H
Ciofini
Ilaria
I
Adamo
Carlo
C
André
Jean-Marie
JM
Perpète
Eric A
EA