S66x8 Noncovalent Interactions Revisited: New Benchmark and Performance of Composite Localized Coupled-Cluster Methods

TL;DR

This study reevaluates the S66x8 noncovalent interactions benchmark with high-level methods, assesses localized coupled-cluster approaches, and identifies the most accurate computational strategies for noncovalent interaction energies.

Contribution

It provides a revised benchmark for S66x8 interactions and evaluates the performance of various localized coupled-cluster methods and composite schemes.

Findings

LNO-CCSD(T) performs well without BSSE correction but needs extrapolation or composite schemes.

PNO-LCCSD(T) is most effective with counterpoise correction.

Economical methods like dRPA75-D3BJ and certain DFT functionals show high accuracy.

Abstract

The S66x8 noncovalent interactions benchmark has been re-evaluated at the "sterling silver" level, using explicitly correlated MP2-F12 near the complete basis set limit, CCSD(F12*)/aug-cc-pVTZ-F12, and a (T) correction from conventional CCSD(T)/sano-V{D,T}Z+ calculations. The revised reference value disagrees by 0.1 kcal/mol RMS with the original Hobza benchmark and its revision by Brauer et al, but by only 0.04 kcal/mol variety from the "bronze" level data in Kesharwani et al., Aust. J. Chem. 71, 238-248 (2018). We then used these to assess the performance of localized-orbital coupled cluster approaches with and without counterpoise corrections, such as PNO-LCCSD(T) as implemented in MOLPRO, DLPNO-CCSD (T1) as implemented in ORCA, and LNO-CCSD(T) as implemented in MRCC, for their respective "Normal", "Tight", and "very Tight" settings. We also considered composite approaches combining different basis sets and cutoffs. Furthermore, in order to isolate basis set convergence from domain truncation error, for the aug-cc-pVTZ basis set we compared PNO, DLPNO, and LNO approaches with canonical CCSD(T). We conclude that LNO-CCSD(T) with veryTight criteria performs very well for "raw" (CP-uncorrected), but struggles to reproduce counterpoise-corrected numbers even for veryVeryTight criteria: this means that accurate results can be obtained using either extrapolation from basis sets large enough to quench basis set superposition error (BSSE) such as aug-cc-pV{Q,5}Z, or using a composite scheme such as Tight{T,Q}+1.11[vvTight(T) - Tight(T)]. In contrast, PNO-LCCSD(T) works best with counterpoise, while performance with and without counterpoise is comparable for DLPNO-CCSD(T1). Among more economical methods, the highest accuracies are seen for dRPA75-D3BJ, {\omega}B97M-V, {\omega}B97M(2), revDSD-PBEP86-D4, and DFT(SAPT) with a TDEXX or ATDEXX kernel.