The S66 noncovalent interactions benchmark reconsidered using explicitly correlated methods near the basis set limit

Abstract

The S66 benchmark for noncovalent interactions has been re-evaluated using explicitly correlated methods with basis sets near the one-particle basis set limit. It is found that post-MP2 "high-level corrections" are treated adequately well using a combination of CCSD(F12*) with (aug-)cc-pVTZ-F12 basis sets on the one hand, and (T) extrapolated from conventional CCSD(T)/heavy-aug-cc-pV{D,T}Z on the other hand. Implications for earlier benchmarks on the larger S66x8 problem set in particular, and for accurate calculations on noncovalent interactions in general, are discussed. At a slight cost in accuracy, (T) can be considerably accelerated by using sano-V{D,T}Z+ basis sets, while half-counterpoise CCSD(F12*)(T)/cc-pVDZ-F12 offers the best compromise between accuracy and computational cost.

Australian Journal of Chemistry, in press [Graham S. Chandler special issue]

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Cited by in corpus (10)

• Interactions between Large Molecules: Puzzle for Reference Quantum-Mechanical Methods
• What types of chemical problems benefit from density-corrected DFT? A probe using an extensive and chemically diverse test suite
• S66x8 Noncovalent Interactions Revisited: New Benchmark and Performance of Composite Localized Coupled-Cluster Methods
• Prototypical pi-pi dimers re-examined by means of high-level CCSDT(Q) composite ab inito methods
• Performance of Localized-Orbital Coupled Cluster Approaches for the Conformational Energies of Longer n-alkane Chains
• Systematic discrepancies between reference methods for non-covalent interactions within the S66 dataset
• Automatic generation of complementary auxiliary basis sets (CABS) for explicitly correlated methods
• The S66 Noncovalent Interaction Benchmark Re-examined: Composite Localized Coupled Cluster Approaches
• MP2-F12 basis set convergence near the complete basis set limit: are $h$ functions sufficient?
• The Conundrum of Diffuse Basis Sets: A Blessing for Accuracy yet a Curse for Sparsity