Improved DFT Description of Intrastrand Cross-Link Formation by Inclusion of London Dispersion Corrections

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• 作者：C茅line Dupont ; Chandan Patel ; Elise Dumont
• 刊名：Journal of Physical Chemistry B
• 出版年：2011
• 出版时间：December 22, 2011
• 年：2011
• 卷：115
• 期：50
• 页码：15138-15144
• 全文大小：862K
• 年卷期：v.115,no.50(December 22, 2011)
• ISSN：1520-5207

文摘

The formation of covalent linkages between two vicinal nucleotides has been proved experimentally to constitute a particularly deleterious class of DNA lesions. These tandem lesions by essence present a competitive chemistry. The density functional theory with dispersion (DFT-D) method is shown to dramatically improve the theoretical description of the formation of a prototypical intrastrand cross-link, when compared to pure or hybrid GGA functionals which strongly deviate from the 蟺鈥撓€ self-stacking mode, as dinucleotides are artificially stabilized by the formation of unrealistic intramolecular hydrogen bonds (HBs). Inclusion of London dispersion correction restores a more realistic picture of the reactant structure and also of geometries and energies along the reaction profile. This paves the way toward a robust insilico screening of intrastrand cross-link DNA defects.