Accurate full configuration interaction correlation energy estimates for five- and six-membered rings.

Abstract

Following our recent work on the benzene molecule [P.-F. Loos, Y. Damour, and A. Scemama, J. Chem. Phys. 153, 176101 (2020)], motivated by the blind challenge of Eriksen et al. [J. Phys. Chem. Lett. 11, 8922 (2020)] on the same system, we report accurate full configuration interaction (FCI) frozen-core correlation energy estimates for 12 five- and six-membered ring molecules (cyclopentadiene, furan, imidazole, pyrrole, thiophene, benzene, pyrazine, pyridazine, pyridine, pyrimidine, s-tetrazine, and s-triazine) in the standard correlation-consistent double-ζ Dunning basis set (cc-pVDZ). Our FCI correlation energy estimates, with an estimated error smaller than 1 millihartree, are based on energetically optimized-orbital selected configuration interaction calculations performed with the configuration interaction using a perturbative selection made iteratively algorithm. Having at our disposal these accurate reference energies, the respective performance and convergence properties of several popular and widely used families of single-reference quantum chemistry methods are investigated. In particular, we study the convergence properties of (i) the Møller-Plesset perturbation series up to fifth-order (MP2, MP3, MP4, and MP5), (ii) the iterative approximate coupled-cluster series CC2, CC3, and CC4, and (iii) the coupled-cluster series CCSD, CCSDT, and CCSDTQ. The performance of the ground-state gold standard CCSD(T) as well as the completely renormalized CC model, CR-CC(2,3), is also investigated. We show that MP4 provides an interesting accuracy/cost ratio, while MP5 systematically worsens the correlation energy estimates. In addition, CC3 outperforms CCSD(T) and CR-CC(2,3), as well as its more expensive parent CCSDT. A similar trend is observed for the methods including quadruple excitations, where the CC4 model is shown to be slightly more accurate than CCSDTQ, both methods providing correlation energies within 2 millihartree of the FCI limit.