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In this article we use MP2 and CCSD(T) calculations for the A24 and S66 data sets to explore how midbond functions can be used to generate cost effective counterpoise corrected supramolecular interaction energies of noncovalent complexes. We use the A24 data set to show that the primary role of midbond functions is not to approach the complete basis set limit, but rather to ensure a balanced description of the molecules and the interaction region (unrelated to the basis set superposition error). The need for balance is a consequence of using atom centered basis sets. In the complete basis set limit, the error will disappear, but reaching the complete basis set limit is not feasible beyond small systems. For S66 we investigate the need for increasing the number of midbond centers. Results show that adding a second midbond center increases the accuracy, but the effect is secondary to changing the atom centered basis set. Further, by comparing calculations using the 3s3p2d1f1g midbond set with using aug‐cc‐pVDZ and aug‐cc‐pVTZ as midbond sets, we see that the requirements for the midbond set to be effective, is not just that it contains diffuse functions, but also that high angular momentum functions are included. By comparing two approaches for placing midbond centers we show that results are not particularly sensitive to placement as long as the placement is reasonable. [ABSTRACT FROM AUTHOR]

Density functional theory, in general, is considered to underesti-mate the weak van der Waals type of intermolecular interactions. We optimized parameters of the local response dispersion (LRD) method applied to the long-range corrected exchange-correlation functionals (LC-B0P12+LRD and LCgau-BOP+LRD) on the interac-tion energy for the complexes in the recently compiled S66 data-base and found to be comparable with the high-level wave function-based methods reported in Rezâc et al. (J. Chem. Theory Comput. 2011, 7, 2427). Our calculations with the S66 intermolec-ular complexes at equilibrium geometries suggests that the LC-B0P12+LRD and LCgau-BOP+LRD are well-balanced and lower cost alternatives to the methods reported in the database. Further, test on the S66X8 database (with eight nonequilibrium points) and the HBC6 and NBC10 database shows LC+LRD method with newly optimized parameters is a promising candidate for dealing such weak interactions. Finally, the new parameterized LC+LRD method was tested on X40 benchmark halogenated complexes. [ABSTRACT FROM AUTHOR]

The relative stability of biologically relevant, hydrogen bonded complexes with shortened distances can be assessed at low cost by the electrostatic multipole term alone more successfully than by ab initio methods. These results imply that atomic multipole moments may help improve ligand-receptor ranking predictions, particularly in cases where accurate structural data are not available. © 2013 Wiley Periodicals, Inc. [ABSTRACT FROM AUTHOR]