About the overestimation of the basis set superposition error on interaction energy calculations for van der Waals systems

Abstract

Articles you may be interested inOn the importance of the fragment relaxation energy terms in the estimation of the basis set superposition error correction to the intermolecular interaction energy A systematic study on the basis set superposition error in the calculation of interaction energies of systems of biological interest J. Chem. Phys. 90, 6361 (1989); 10.1063/1.456353 Correction of the basis set superposition error in SCF and MP2 interaction energies. The water dimer J. Chem. Phys. 84, 6328 (1986); 10.1063/1.450725 Systematic study of basis set superposition errors in the calculated interaction energy of two HF moleculesA procedure to estimate the basis set superposition error is proposed avoiding the overestimation of the counterpoise correction in the van der Waals interactions. Numerical calculations were carried out in the Ne· .. Ne complex at the SCF level.

The decomposition of the SCF interaction energy in hydrogen bonded dimers corrected for basis set superposition errors: An examination of the basis set dependence

“…5): the addition of polarization functions does not produce, per se, a noticeable change in the charge transfer contributions nor in the corresponding BSSE'S. The proposal of reducing CP corrections to the polarization functions of the partners, as recently advocated [31,32], is not justified by the present calculations. We stress however that these considerations hold for the class of intermediate hydrogen bonds: with a different chemical composition of the system (e.g., a couple of rare gas atoms), the conclusions could be different.…”

Energy decomposition analysis approaches and their evaluation on prototypical protein–drug interaction patterns

“…Secondly, it is theoretically possible for the charge transfer contribution to be repulsive on inclusion of the CP BSSE correction. This is because the CP correction has a tendency to overestimate the BSSE 171,172 as discussed above. As noted by Mo et al, 11 it may be appropriate to consider the ALMO (and BLW) EDA charge transfer energies with and without the BSSE energy correction as the upper and lower bounds of this energy.…”

“…Our general observations of the schemes are summarised in Table 2. 6.2.8.1 General observations. The CP correction is known to overestimate the BSSE 171,172 and many of the schemes we have included in our investigation apply the CP correction to energy terms. It is important to note that as a result this correction has the potential to give rise to unphysical results, as is observed in the case of the charge transfer energies in the group 1 metal ion interacting systems of test set 2 for example.…”

Weak interactions between small systems. Models for studying the nature of intermolecular forces and challenging problems for ab initio calculations

“…187,188 In support of this philosophy there have been presented numerical examples in which results obtained by the Boys and Bernardi CP method were too repulsive in comparison with experimental or basis-set-saturated results. 128,187,[189][190][191] In view of this objection, Daudey et of each monomer with a monomer-centered basis set augmented only by the virtual orbitals of the partner.…”