MERCE：面向高阶耦合簇精度的方法空间相关能外推法
MERCE: Method-Space Correlation Energy Extrapolation toward High-Rank Coupled Cluster Accuracy
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中文总结 AI 辅助
本文提出MERCE框架，通过为MP2和CCSD(T)分配自适应有效秩并拟合三点外推形式，可降低CCSD(T)误差，优于高阶耦合簇基线，且具备良好可迁移性。
中文摘要 AI 辅助
能量外推是一种成熟的策略，可在无需进行成本过高的计算的情况下逼近量子化学极限。完全基组外推法已被广泛应用，而跨电子结构方法的外推法发展则滞后得多。本文提出方法空间有效秩相关能外推法（MERCE），这是一种自适应有效秩框架，用于从二阶Møller-Plesset微扰理论（MP2）、含单双激发的耦合簇方法（CCSD）及含微扰三重激发的CCSD（CCSD(T)）中估计高阶有限基组相关能。该方法从局域MP2-CCSD-CCSD(T)相关能模式为MP2和CCSD(T)分配自适应有效秩，并为每个体系拟合紧凑的三点外推形式。分层模型选择协议平衡了跨数据集可迁移性、最大数据集级平均绝对误差（MAE）比值、以全组态相互作用（FCI）为参考的开发集鲁棒性、尺寸一致性缺陷及A24非共价相互作用能的性能。在模型开发过程中使用的化学多样性基准测试中，选定的MERCE模型大幅降低了CCSD(T)的误差，且常优于所测试的高阶耦合簇基线。在仅冻结函数形式和参数后，进一步评估了可迁移性。利用人工非相互作用对及实际A24和选定的S66组分计算，量化了形式非加和性。
英文摘要
Energy extrapolation is a well-established strategy for approaching quantum-chemical limits without performing prohibitively expensive calculations. Complete basis set extrapolation is widely used, whereas extrapolation across electronic structure methods remains much less developed. Method-Space Effective-Rank Correlation Energy Extrapolation (MERCE) is introduced as an adaptive effective-rank framework for estimating high-rank finite-basis correlation energies from second-order Moller-Plesset perturbation theory (MP2), coupled cluster with single and double excitations (CCSD), and CCSD with perturbative triples [CCSD(T)]. The method assigns adaptive effective ranks to MP2 and CCSD(T) from the local MP2-CCSD-CCSD(T) correlation energy pattern and fits a compact three-point extrapolation form for each system. A hierarchical model-selection protocol balances cross-dataset transferability, maximum dataset-level mean absolute error (MAE) ratios, robustness on developmental sets referenced to full configuration interaction (FCI), size-consistency defects, and performance for A24 noncovalent interaction energies. Across the chemically diverse benchmarks used during model development, the selected MERCE model substantially reduces CCSD(T) errors and frequently improves upon the tested higher-rank coupled cluster baselines. Transferability is further assessed using calculations performed only after the functional form and parameters were frozen. Formal nonadditivity is quantified using artificial noninteracting pairs and the actual A24 and selected S66 component calculations.
发表机构
- Nicolaus Copernicus University in Toruń（托伦哥白尼大学）
- Xiamen University（厦门大学）
- Aitomistic
机构由 AI 辅助整理，请以论文原文为准。
