Basis set superposition error in MP2 and density-functional theory: A case of methane-nitric oxide association

Abstract

A systematic study of basis set superposition error (BSSE) behavior in H(3)C-H[ellipsis (horizontal)][NO] complexes for both -H...N- and -H...O- orientations were carried out using MP2 and density-functional theory with Pople's [6-31G(d,p),6-311++G(nd,nd), where n=1,2,3, and 6-311++G(3df,3pd)] and Dunning's augmented correlation consistent basis sets [aug-cc-pVXZ (X=D and T)]. Corrected and uncorrected counterpoise potential-energy surfaces (PESs) were explored and differences obtained between them indicate that reliable optimizations of these molecular interactions must be carried out in a PES free of BSSE, even in the case of large basis sets and popularly used functionals such as B3LYP. Although all basis used could be always considered within a margin of approximation for representing molecular orbitals and show important values of BSSE, 6-311++G(2d,2p) basis set shows the best results in uncorrected PES with respect to the corrected ones. B3LYP functional produces erratic results: complexes appear repulsive and the intermolecular distances are always large, evidencing the lack of a correct dispersive forces treatment in the original parameterization. According to the MP2 results, the -H...N- interactions appear as slightly more stable than those of the -H...O- orientation.

Analysis of the basis set superposition error in molecular dynamics of hydrogen-bonded liquids: Application to methanol

“…It has been shown that the calculation of the BSSE corrections can change their potential energy curves and surfaces, [58][59][60][61][62] and can alter the bond distances. 58,60,61,63,64 It is well known that BSSE can be a significant fraction of the binding energy of the water dimer, which could affect liquid simulations.…”

Molecular orbital model of the influence of interaction between O2 and aluminosilicate sites on the triplet–singlet energy gap and reactivity

“…We decided to use MP2 [37] due to the unpredictable behavior of some KS-DFT functionals in the case of very weak intermolecular complexes [38,39]. The selection of basis sets is a difficult point.…”

“…Single-point calculations with MP2/6-311++g (2d,2p) have been also carried out using the optimized structures obtained with the MP2/6-311G(d,p) level of theory. This basis set has a good performance for other weak complexes of open-shell systems previously studied by us [39]. Full structure optimizations of the clusters were performed without geometry restriction or fixed coordinates.…”

Efficient model chemistries for peptides. I. General framework and a study of the heterolevel approximation in RHF and MP2 with Pople split‐valence basis sets

“…Apart from the approximations described above, which are the most commonly used and the only ones that are considered in this work, the MC concept may include a lot of additional features: protocols for extrapolating to the infinite-basis set limit [65][66][67][68][69], additivity assumptions [70][71][72][73], extrapolations of the Møller-Plesset series to infinite order [74], removal of the so-called basis set superposition error (BSSE) [75][76][77][78][79][80][81], etc. The reason behind most of these techniques is the urging need to reduce the computational cost of the calculations.…”