Damour Yann, Véril Mickaël, Kossoski Fábris, Caffarel Michel, Jacquemin Denis, Scemama Anthony, Loos Pierre-François
Laboratoire de Chimie et Physique Quantiques (UMR 5626), Université de Toulouse, CNRS, UPS, Toulouse, France.
Université de Nantes, CNRS, CEISAM UMR 6230, F-44000 Nantes, France.
J Chem Phys. 2021 Oct 7;155(13):134104. doi: 10.1063/5.0065314.
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.
继我们最近关于苯分子的研究工作[P.-F. 卢斯、Y. 达穆尔和A. 斯凯马马，《化学物理杂志》153, 176101 (2020)]之后，受埃里克森等人[《物理化学快报》11, 8922 (2020)]对同一体系的盲测挑战的启发，我们报告了在标准的相关一致双ζ邓宁基组（cc-pVDZ）下，对12个五元环和六元环分子（环戊二烯、呋喃、咪唑、吡咯、噻吩、苯、吡嗪、哒嗪、吡啶、嘧啶、s-四嗪和s-三嗪）的精确全组态相互作用（FCI）冻结核相关能估计。我们的FCI相关能估计值的误差估计小于1毫哈特里，这些估计基于使用迭代微扰选择算法进行的能量优化轨道选择组态相互作用计算。有了这些精确的参考能量后，我们研究了几种常用且广泛使用的单参考量子化学方法各自的性能和收敛性质。特别地，我们研究了以下几种方法的收敛性质：(i) 直至五阶的莫勒-普莱斯特定则微扰级数（MP2、MP3、MP4和MP5），(ii) 迭代近似耦合簇级数CC2、CC3和CC4，以及(iii) 耦合簇级数CCSD、CCSDT和CCSDTQ。还研究了基态金标准CCSD(T)以及完全重整化的CC模型CR-CC(2,3)的性能。我们表明MP4提供了有趣的精度/成本比，而MP5系统性地恶化了相关能估计。此外，CC3优于CCSD(T)和CR-CC(2,3)，以及比其更昂贵的母体CCSDT。对于包含四重激发的方法也观察到类似趋势，其中CC4模型显示比CCSDTQ略精确，两种方法提供的相关能都在FCI极限的2毫哈特里以内。
