Can TD-DFT calculations accurately describe the excited states behavior of stacked nucleobases? The cytosine dimer as a test case

✍ Scribed by Fabrizio Santoro; Vincenzo Barone; Roberto Improta

• Publisher: John Wiley and Sons
• Year: 2008
• Tongue: English
• Weight: 300 KB
• Volume: 29
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20853

✦ Synopsis

Abstract

By using calculations rooted in the time dependent density functional theory (TD‐DFT) we have investigated how the lowest energy excited states of a face‐to‐face π‐stacked cytosine dimer vary with the intermonomer distance (R). The perfomances of different density functionals have been compared, focussing mainly on the lowest energy single excited state of the dimer (S~1~)~2~. TD‐PBE0, TD‐LC‐ωPBE, and TD‐M05‐2X provide a picture very similar to that obtained at the CASPT2 level by Merchan et al. (J Chem Phys 2006, 125, 231102), predicting that (S~1~)~2~ has a minimum for R ∼ 3 Å, with a binding energy of ∼0.5 eV, whereas TD‐B3LYP, TD‐CAM‐B3LYP, and TD‐PBE understimate the binding energy. However, independently of the functional employed, no low‐energy spurious charge transfer transitions are predicted by TD‐DFT calculations, also when a nonsymmetric dimer is investigated, providing encouraging indications for the use of TD‐DFT for studying the excited state of π‐stacked nucleobases. © 2007 Wiley Periodicals, Inc. J Comput Chem 2008