Assessment of PBE0 for evaluating the absorption spectra of carbonyl molecules |
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Authors: | Valérie Wathelet Julien Preat Michaël Bouhy Michèle Fontaine Eric A Perpète Jean-Marie André Denis Jacquemin |
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Institution: | Laboratoire de Chimie Théorique Appliquée, Facultés Universitaires Notre-Dame de la Paix, rue de Bruxelles 61, B-5000 Namur, Belgium |
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Abstract: | 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. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 |
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Keywords: | absorption spectra TD‐DFT carbonyls PBE0 Woodward– Fieser rules |
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