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Efficient bond function basis set for π‐π interaction energies
Author(s) -
Ding Yun,
Mei Ye,
Zhang John Z. H.,
Tao FuMing
Publication year - 2007
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.20788
Subject(s) - basis set , basis (linear algebra) , chemistry , valence bond theory , basis function , bond order , bond energy , perturbation theory (quantum mechanics) , generalized valence bond , bond length , function (biology) , computational chemistry , atomic physics , physics , quantum mechanics , mathematics , molecule , density functional theory , geometry , molecular orbital , evolutionary biology , biology
Systematic study has been carried out to investigate the accuracy of mid‐bond functions in describing π‐π interactions in benzene dimer. Potential energy curves are calculated for the sandwich, T‐shaped, and parallel‐displaced configurations of benzene dimer by adding bond functions in MP2 (second‐order Møller–Plesset perturbation theory) calculations with a wide range of split‐valence and augmented, correlation‐consistent basis sizes. At MP2 level, the largest basis set used with a bond function (denoted aug‐cc‐pVDZf‐6s6p4d2f) differs by only ∼0.1 kcal/mol relative to the result obtained from the standard aug‐cc‐pVQZ basis calculation (without the bond function). The calculated potential energy curves from the bond function basis aug‐cc‐pVDZf‐6s6p4d2f and the larger standard basis aug‐cc‐pVTZ are in excellent agreement with each other for all three configurations. The number of bond function basis aug‐cc‐pVDZf‐6s6p4d2f is 526 compared to 828 of aug‐cc‐pVTZ and 1512 of aug‐cc‐pVQZ. Current study shows that bond functions can be effectively employed to give accurate description of π‐π interactions with the addition of only a minimal number of bond functions. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008