Evaluation of DFT methods to study reactions of benzene with OH radical

✍ Scribed by Steve Scheiner

• Book ID: 104577224
• Publisher: John Wiley and Sons
• Year: 2011
• Tongue: English
• Weight: 850 KB
• Volume: 112
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.23089

✦ Synopsis

Abstract

Several density functional theory” (DFT) methods are applied to two different reaction channels involving OH^•^ + C~6~H~6~, and the results compared with high‐level ab initio calculations. The OH^•^ adds directly to one C atom in the first channel, first forming an encounter complex with the OH^•^ poised above the aromatic plane. B3LYP, BH&HLYP, and MPW1K compute an accurate estimate of the overall exothermicity, whereas M05‐2X, PBE0, and PBEPBE overestimate this quantity to some degree. With the exceptions of PBEPBE and PBE0, the other methods produce an acceptable barrier to addition. All approaches except BH&HLYP correctly predict an exothermic H^•^ abstraction, although PBEPBE is too exothermic. The BH&HLYP barrier to H^•^ abstraction is too high while the MPW1K, PBE0, and B3LYP values are better, and M05‐2X the best. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011