跨分子与周期体系的约化密度矩阵泛函理论：筛选与耦合优化
Reduced Density Matrix Functional Theory Across Molecules and Periodic Systems: Screening and Coupled Optimization
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中文总结 AI 辅助
本研究开发了周期体系的RDMFT耦合优化实现，结合短程筛选得到可迁移泛函，提升了优化效率与能量精度，其性能优于半局域和杂化密度泛函。
中文摘要 AI 辅助
约化密度矩阵泛函理论（RDMFT）为处理强电子关联提供了严谨框架，但其在周期体系中的应用长期受两个基础挑战阻碍：缺乏可迁移的近似泛函，以及轨道占据优化效率低下。本文表明这两个长期难题可同时攻克。我们开发了基于耦合优化框架的RDMFT周期实现，该框架能在周期边界条件下高效同时优化自然轨道与占据数。利用该实现，我们证明物理驱动的短程筛选可将Power泛函转化为适用于分子与周期固体的可迁移泛函。值得注意的是，短程筛选具有双重作用：除大幅提升能量精度外，还从根本上重塑优化空间，产生稳健的优化步长并显著加速收敛。耦合优化框架在周期计算中所需的优化迭代次数始终远少于传统解耦优化，而经筛选的ωP22泛函在预测代表性表面反应能垒方面优于半局域和杂化密度泛函。这些结果构建了计算高效的周期RDMFT框架，并确定短程筛选是开发可迁移一体约化密度矩阵泛函的有前景设计原则。
英文摘要
Reduced density matrix functional theory (RDMFT) provides a rigorous framework for treating strong electron correlation, yet its application to periodic systems has long been hindered by two fundamental challenges: the lack of transferable approximate functionals and the poor efficiency of orbital-occupation optimization. Here we show that these two longstanding obstacles can be overcome simultaneously. We develop a periodic implementation of RDMFT based on a coupled optimization framework that enables the efficient simultaneous optimization of natural orbitals and occupation numbers under periodic boundary conditions. Using this implementation, we demonstrate that physically motivated short-range screening transforms the Power functional into a transferable functional applicable to both molecules and periodic solids. Remarkably, short-range screening is found to play a dual role: besides substantially improving energetic accuracy, it fundamentally reshapes the optimization landscape, producing robust optimization step sizes and dramatically accelerating convergence. The coupled optimization framework consistently requires substantially fewer optimization iterations than conventional decoupled optimization for periodic calculations, while the screened $ω$P22 functional outperforms semilocal and hybrid density functionals in predicting representative surface reaction barriers. These results establish a computationally efficient periodic RDMFT framework and identify short-range screening as a promising design principle for developing transferable one-body reduced-density-matrix functionals.
