发表机构
Max Planck Institute for Solid State Research; Yusuf Hamied Department of Chemistry, University of Cambridge; Scientific Computing Center, Karlsruhe Institute of Technology（马克斯·普朗克固体研究所; 剑桥大学尤瑟夫·哈米德化学系; 卡尔斯鲁厄理工学院科学计算中心）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本文首次将transcorrelated耦合簇理论应用于非共价相互作用，在A24数据集上验证了xTC-CCSD(T)方法的准确性，并展示了其在氢键和色散体系中的潜力。
AI 中文摘要
我们提出了transcorrelated (TC) 耦合簇 (CC) 理论在xTC近似下对非共价相互作用的首次应用。该方法在包含氢键、混合和纯色散束缚二聚体的A24数据集上进行了评估。xTC相互作用能在CCSD、DCSD和CCSD(T)水平上，使用aug-cc-pVDZ (AVDZ) 和 aug-cc-pVTZ (AVTZ) 基组进行计算，并与正则和显式相关的F12方法进行了比较。由于非共价相互作用能依赖于二聚体和单体之间微妙的误差抵消，我们为每个二聚体优化TC Jastrow因子，并在相应的单体计算中重用相同的参数。这种共享参数策略减少了随机优化噪声，否则该噪声将主导相互作用能。结果表明，xTC-CCSD(T)/AVTZ方法在氢键体系中表现极佳，相对于使用CCSD(T)/CBS + ΔCCSDT(Q) + 核修正生成的基准值，相互作用能的平均绝对误差仅为0.007 kcal/mol。对于纯色散束缚体系，误差略大（0.055 kcal/mol），导致整个数据集的总体MAE为0.030 kcal/mol。将ΔMP2修正添加到xTC-CCSD(T)/AVDZ中，使这些结果接近AVTZ质量，并为更大的非共价体系提供了实用途径。将xTC相互作用能分解为平均场和关联贡献表明，关联贡献的一部分被TC方法系统地转移到平均场贡献中。这一物理上吸引人的特性表明，TC方法在非共价相互作用的定量描述方面具有巨大潜力，并为高精度量子化学应用于生物和软物质感兴趣的系统开辟了新途径。
英文摘要
We present the first application of transcorrelated (TC) coupled-cluster (CC) theory to noncovalent interactions within the xTC approximation. The method is assessed for the A24 dataset of hydrogen-bonded, mixed and pure dispersion bound dimers. The xTC interaction energies are computed at the CCSD, DCSD, and CCSD(T) levels in aug-cc-pVDZ (AVDZ), aug-cc-pVTZ (AVTZ) basis sets, and are compared with both canonical and explicitly correlated F12 methods. Because non-covalent interaction energies rely on delicate error cancellation between dimers and monomers, we optimize the TC Jastrow factor for each dimer, and reuse the same parameters for the corresponding monomer calculations. This shared-parameter strategy reduces stochastic optimization noise which would otherwise dominate the interaction energies. The results show that the xTC-CCSD(T)/AVTZ method performs extremely well for the hydrogen-bonded systems, with a mean-absolute error of only 0.007 kcal/mol in the interaction energies, with respect to the benchmark values generated with CCSD(T)/CBS + $Δ$CCSDT(Q) + core corrections. For pure dispersion bound systems the errors are slightly larger (0.055 kcal/mol), leading to an overall MAE of 0.030 kcal/mol for the entire dataset. Adding a $Δ$MP2 correction to the xTC-CCSD(T)/AVDZ brings these results close to AVTZ quality and provides a practical route toward larger noncovalent systems. A decomposition of the xTC interaction energy into a mean-field and correlation contribution shows that part of the correlation contribution is systematically shifted by the TC method to the mean-field contribution. This physically appealing feature indicates that the TC method has great potential for the quantitative description of noncovalent interactions, and opens a new route for high-accuracy quantum chemistry to be applied to systems of biological and soft-matter interest.
