Symmetry-adapted perturbation theory (SAPT) based on coupled cluster approach with single and double excitations (CCSD) treatment of intramonomer electron correlation effects was applied to study rare gas homodimers from He₂ to Kr₂. The obtained benchmark CCSD-SAPT energies, including cumulant contributions to first order exchange and second-order exchange-induction terms, were then compared to their counterparts found using other methods—Møller-Plesset-SAPT based on many-body Møller-Plesset perturbation theory and DFT-SAPT based on density functional theory. The SAPT terms up to the second-order were calculated with the basis sets close to the complete basis set at the large range of interatomic distances R. It was shown that overestimation of the binding energies D_e found with DFT-SAPT reported in the work of Shirkov and Makarewicz [J. Chem. Phys. 142, 064102 (2015)] for Ar₂ and Kr₂ is mostly due to underestimation of the exchange energy $E_{\text{exch}}^{(1)}$ when comparing to the CCSD-SAPT benchmark. The CCSD-SAPT potentials were found to give the following values of the dissociation energies D₀: 0.0006 cm⁻¹ for He₂, 16.71 cm⁻¹ for Ne₂, 85.03 cm⁻¹ for Ar₂, and 129.81 cm⁻¹ for Kr₂, which agree well with the values found from previously reported highly accurate ab initio supermolecular potentials and experimental data. The long-range dispersion coefficients C_2n up to n = 6 that give the dispersion energy asymptotically equivalent to its SAPT counterpart were calculated from dynamic multipole polarizabilities at different levels of theory.

中文翻译：

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与MP-SAPT和DFT-SAPT进行比较的CCSD-SAPT稀有气体二聚体基准研究

基于单簇和双激发（CCSD）耦合簇方法的对称适应扰动理论（SAPT）处理单体内电子相关效应，研究了稀有气体同二聚体从He ₂到Kr ₂。然后将获得的基准CCSD-SAPT能量（包括对一阶交换和二阶交换-感应项的累积贡献）与使用其他方法（基于多体Møller-Plesset微扰理论的Møller-Plesset-SAPT）找到的对应能量进行比较。基于密度泛函理论的DFT-SAPT。在大原子间距离R的情况下，使用接近于完整基础集的基础集来计算直至二阶的SAPT项。结果表明，在Shirkov和Makarewicz的工作中报道了用DFT-SAPT发现的结合能D _e的高估[J．化学 物理 142，064102（2015）]作为Ar ₂和氪₂主要是由于交换能的低估$E_{\text{放出}}^{（\mathrm{1个}）}$与CCSD-SAPT基准进行比较时。的CCSD-SAPT电位被发现，得到离解能的下列值ð ₀：0.0006厘米^-1为赫₂，16.71厘米^-1为氖₂，85.03厘米^-1作为Ar ₂，和129.81厘米^-1为氪_{如图2所示}，其与从先前报道的高度准确的从头算起的超分子势和实验数据中发现的值非常吻合。长程扩散系数c ^ _{2 Ñ}高达Ñ 从理论上不同水平的动态多极极化率计算出= 6，其色散能量渐近地等于其SAPT对应物。