Post-CCSD(T) contributions to total atomization energies in multireference systems Available to Purchase

We examine the magnitude and the basis set convergence of post-coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) contributions (up to CCSDTQ567) for a wide and diverse set of 21 first- and second-row molecules with up to four non-hydrogen atoms. We focus on multireference systems for which post-CCSD(T) effects are particularly pronounced. The considered molecules are BN(¹∑⁺), C₂(¹∑⁺), O₂, FO, P₂, S₂, ClO, N₂O, NO₂, O₃, FNO, FO₂, F₂O, S₂O, S₃, ClNO, ClOO, Cl₂O, N₂C₂, P₄, and S₄. This set spans the gamut from molecules dominated by moderate nondynamical correlation (e.g., FO, ClO, NO₂, S₂O, N₂C₂, and P₄) to systems dominated by strong nondynamical correlation (e.g., BN, C₂, FO₂, O₃, ClOO, and S₄). We examine the basis set convergence of the CCSDT, CCSDT(Q), CCSDTQ, CCSDTQ(5), CCSDTQ5, CCSDTQ5(6), CCSDTQ56, CCSDTQ56(7), and CCSDTQ567 methods. The largest basis sets employed in each category are cc-pV6Z (CCSDT(Q)), cc-pV5Z (CCSDTQ), cc-pVTZ (CCSDTQ5(6)), and cc-pVDZ (CCSDTQ567). Apart from examining the basis-set convergence of post-CCSD(T) contributions near the one-particle basis-set limit, this work explores cost-effective approaches for obtaining these contributions from fairly small basis sets. We consider both effective basis-set extrapolations and scaling factors. An important finding is that extrapolating the perturbative connected quadruples, (Q), from the cc-pVDZ(4s3p1d) and cc-pVTZ basis sets yields near basis-set limit results and represents a significant improvement relative to cc-pV{D,T}Z extrapolation at no additional computational cost (where cc-pVDZ(4s3p1d) is an extended version of the cc-pVDZ basis set). Combining the (Q)/cc-pV{D(4s3p1d),T}Z extrapolations with the fully iterative connected quadruples, Q–(Q), contribution calculated with the cc-pVDZ (or even the cc-pVDZ(3s2p)) basis set is a cost-effective way for obtaining the connected quadruples component close to the basis-set limit (where cc-pVDZ(3s2p) is a truncated version of the cc-pVDZ basis set). In addition, we show that the (5)/cc-pVDZ(3s2p) and (6)/cc-pVDZ(3s2p) components provide reasonable approximations for the connected quintuple and sextuple components close to the basis-set limit, respectively.