Assessment of PBEO for evaluating the absorption spectra of carbonyl molecules

摘要

Using the parameter-free PBE0 hybrid functional, we compute the UV/Vis spectra of a series of solvated compounds presenting a carbonyl chromophoric unit linked to a carbon-carbon double bond. It turns out that PBE0 is extremely efficient for accurately reproducing experimental values, with a mean unsigned error of 7 nm for an extended set of compounds, although no fitting or statistical treatments are performed. PBE0 has a predictive efficiency comparable to the well-known Woodward-Fieser empirical formula, and can therefore be used to extend these rules without requiring additional experimental results. Consequently, the UV/Vis spectra of several compounds that have not yet been synthesized are predicted. (c) 2006 Wiley Periodicals, Inc. Int J Quantum Chem 106: 1853-1859, 2006.