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Hybrid density functional theory for π‐stacking interactions: Application to benzenes, pyridines, and DNA bases
Author(s) -
Waller Mark P.,
Robertazzi Arturo,
Platts James A.,
Hibbs David E.,
Williams Peter A.
Publication year - 2006
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20363
Subject(s) - density functional theory , stacking , dimer , benzene , chemistry , intermolecular force , water dimer , nucleobase , computational chemistry , hybrid functional , range (aeronautics) , quantum , electron density , dna , electron , chemical physics , molecule , hydrogen bond , quantum mechanics , physics , materials science , organic chemistry , biochemistry , composite material
The suitability of a hybrid density functional to qualitatively reproduce geometric and energetic details of parallel π‐stacked aromatic complexes is presented. The hybrid functional includes an ad hoc mixture of half the exact (HF) exchange with half of the uniform electron gas exchange, plus Lee, Yang, and Parr's expression for correlation energy. This functional, in combination with polarized, diffuse basis sets, gives a binding energy for the parallel‐displaced benzene dimer in good agreement with the best available high‐level calculations reported in the literature, and qualitatively reproduces the local MP2 potential energy surface of the parallel‐displaced benzene dimer. This method was further critically compared to high‐level calculations recently reported in the literature for a range of π‐stacked complexes, including monosubstituted benzene–benzene dimers, along with DNA and RNA bases, and generally agrees with MP2 and/or CCSD(T) results to within ±2 kJ mol −1 . We also show that the resulting BH&H binding energy is closely related to the electron density in the intermolecular region. The net result is that the BH&H functional, presumably due to fortuitous cancellation of errors, provides a pragmatic, computationally efficient quantum mechanical tool for the study of large π‐stacked systems such as DNA. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 491–504, 2006