基于材料约束原子优化的铜固体相关一致高斯基组
Correlation-consistent Gaussian basis sets for copper solids from material-constrained atomic optimization
AI总结：
研究针对相关一致高斯基组在铜固体应用中的问题，引入材料约束原子优化框架，生成多种处理的Cu基组，保持数值稳定性，重现相关性质，并通过计算评估多种误差，为CO吸附难题提供高斯基基准。
AI中文摘要：
相关一致高斯基组对系统分子量子化学至关重要，但在周期性固体中的直接应用常受弥散原子优化基元严重线性相关的限制，在金属及含金属系统中问题尤为突出。本文引入材料约束原子优化（MCAO）框架，在惩罚代表性固体中重叠矩阵大条件数的同时，保留高斯基组的原子和相关一致特性。作为概念验证，生成了Cu的Dunning风格MCAO - cc - pVXZ基组并进行多种处理。所得基组对Cu固体和表面保持数值稳定性，重现了分子Cu二聚体能量和块状Cu的平面波参考性质。CBS外推随机相位近似计算有助于评估块状Cu和Cu(111)上CO吸附的赝势、相对论和基组误差，为CO吸附难题提供了标量相对论全电子高斯基基准。
英文摘要：
Correlation-consistent Gaussian basis sets are central to systematic molecular quantum chemistry, but their direct use in periodic solids is often limited by severe linear dependence from diffuse atomically optimized primitives. This problem is particularly acute for metallic and metal-containing systems, where reliable complete-basis-set (CBS) extrapolation is needed for correlated-wavefunction benchmarks. We introduce material-constrained atomic optimization (MCAO), a basis-set optimization framework that preserves the atomic and correlation-consistent character of Gaussian basis sets while penalizing large overlap-matrix condition numbers in representative solids. As a proof of concept, we generate Dunning-style MCAO-cc-pVXZ basis sets (X = D, T, Q) for Cu with all-electron, scalar-relativistic all-electron, effective core potential (ECP), and pseudopotential treatments. The resulting basis sets remain numerically stable for Cu solids and surfaces while reproducing molecular Cu dimer energetics and plane-wave reference properties of bulk Cu. CBS-extrapolated random-phase approximation calculations further enable a controlled assessment of pseudopotential, relativistic, and basis-set errors in bulk Cu and CO adsorption on Cu(111), providing scalar-relativistic all-electron Gaussian-basis benchmarks for the CO adsorption puzzle.
