X-ray quality geometries of geodesic polyarenes from theoretical calculations: what levels of theory are reliable?
[structure: see text] Computational methods for calculating molecular geometries have not been well calibrated heretofore against X-ray data for bowl-shaped polycyclic aromatic hydrocarbons (PAHs). The analysis presented here capitalizes on a rare opportunity provided by corannulene to account explicitly for molecular distortions from crystal packing forces. Within the error limits of an extensive X-ray data set, B3LYP/6-31G* calculations were found to correctly reproduce all of the experimental bond distances and bond angles. The reliability and shortcomings of geometry calculations at other levels of theory are enumerated.
Department of Chemistry, University at Albany, State University of New York, Albany, New York 12222-0100, USA. marina@albany.edu
Marina A
MA
Petrukhina
Kristian W
KW
Andreini
James
J
Mack
Lawrence T
LT
Scott