Imaginary vibrational modes in polycyclic aromatic hydrocarbons: a challenging test for the hardness profiles.
In a very recent article (J. Am. Chem. Soc. 2006, 128, 9342-9343) Moran et al. found that electron-correlated methodologies using popular Pople basis sets lead to spurious nonplanar polycyclic aromatic hydrocarbon (PAH) equilibrium structures. Furthermore, some of the present authors have shown that the hardness profiles along a reaction path can be a useful tool to find spurious stationary points in the potential energy surface. Herein, we test the performance of the hardness profiles to detect shortcomings in energy profiles for the challenging case of nonplanar PAHs. The results obtained show that in 41 of the 42 imaginary vibrational modes studied, the hardness profiles indicate the wrong number and type of the potential energy surface stationary points.
Torrent-Sucarrat
Miquel
M
Eenheid Algemene Chemie, Faculteit Wetenschappen, Vrije Universiteit Brussel (VUB), Pleinlaan 2, Brussels, Belgium. mtorrent@vub.ac.be
Geerlings
Paul
P
Luis
Josep M
JM
D000838:Anions / Q000737:chemistry; D003198:Computer Simulation; D006244:Hardness; D015394:Molecular Structure; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D014732:Vibration
D000838:Anions; D011084:Polycyclic Aromatic Hydrocarbons