Collect. Czech. Chem. Commun. 2008, 73, 898-908

Assessment of the Accuracy of TD-DFT Absorption Spectra: Substituted Benzenes

Jean-Marie André*, Denis Jacquemin, Eric A. Perpete, Daniel P. Vercauteren and Valérie Wathelet

Groupe de Chimie-Physique Théorique et Structurale, Facultés Universitaires Notre-Dame de la Paix (FUNDP), rue de Bruxelles, 61, B-5000 Namur, Belgium


Using the parameter-free PBE0 hybrid functional in conjunction with the conducting PCM model, we compute the UV/VIS spectra of a series of solvated phenol and nitrobenzene chromogens. For the first series, the average deviation with respect to experiment is large (about 0.5 eV) but the auxochromic shifts are very accurately and consistently predicted. Therefore, after a statistical treatment, the TD-DFT values are within 0.02 eV of the experimental data. For nitrobenzenes, the average discrepancy is smaller than for phenols, though the impact of individual substitution is much less consistent with experimental trends. We also confirm that push-pull compounds with donor and acceptor groups in meta positions are especially problematic for TD-DFT calculations relying on conventional hybrids, and we unravel the origin of this specific difficulty.

Keywords: Electronic absorption spectroscopy; UV spectroscopy; Nitrobenzene; Phenol; TD-DFT calculations; PBE0 hybrid functional.

References: 31 live references.