Very recently, we introduced a set of correlation consistent effective core potentials (ccECPs) constructed within full many-body approaches. By employing significantly more accurate correlated approaches, we were able to reach a new level of accuracy for the resulting effective core Hamiltonians. We also strived for simplicity of use and easy transferability into a variety of electronic structure methods in quantum chemistry and condensed matter physics. Here, as a reference for future use, we present exact or nearly exact total energy calculations for these ccECPs. The calculations cover H-Kr elements and are based on the state-of-the-art configuration interaction (CI), coupled-cluster (CC), and quantum Monte Carlo (QMC) calculations with systematically eliminated/improved errors. In particular, we carry out full CI/CCSD(T)/CCSDT(Q) calculations with cc-pVnZ with up to n = 6 basis sets and we estimate the complete basis set limits. Using combinations of these approaches, we achieved an accuracy of ≈1-10 mHa for K-Zn atoms and ≈0.1-0.3 mHa for all other elements-within about 1% or better of the ccECP total correlation energies. We also estimate the corresponding kinetic energies within the feasible limit of full CI calculations. In order to provide data for QMC calculations, we include fixed-node diffusion Monte Carlo energies for each element that give quantitative insights into the fixed-node biases for single-reference trial wave functions. The results offer a clear benchmark for future high-accuracy calculations in a broad variety of correlated wave function methods such as CI and CC as well is in stochastic approaches such as real space sampling QMC.

中文翻译：

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精确的原子相关性和相关的总能量，具有一致的有效核心电势。

最近，我们引入了在完整的多体方法中构建的一组相关的一致的有效核心电位（ccECP）。通过采用显着更准确的相关方法，我们能够对产生的有效核心哈密顿量达到更高的精确度。我们还力求在量子化学和凝聚态物理中简化使用并易于转移到各种电子结构方法中。在这里，作为将来使用的参考，我们介绍了这些ccECP的精确或几乎精确的总能量计算。这些计算涵盖了H-Kr元素，并基于最新的组态相互作用（CI），耦合簇（CC）和量子蒙特卡洛（QMC）计算，并系统地消除/改善了误差。尤其是，我们使用cc-pVnZ（最多n = 6个基集）进行完整的CI / CCSD（T）/ CCSDT（Q）计算，并估算完整的基集限制。使用这些方法的组合，我们获得的K-Zn原子的精度约为≈1-10mHa，而所有其他元素的精度约为ccECP总相关能的1％或更好，约为0.1-0.3 mHa。我们还估计了在完全CI计算的可行范围内的相应动能。为了提供用于QMC计算的数据，我们为每个元素包括固定节点扩散蒙特卡洛能量，从而可以定量了解单参考试验波函数的固定节点偏差。