半经典色散修正有效地改进了短程密度泛函动力学关联的多尺度理论
Semiclassical Dispersion Corrections efficiently improve Multi-Configurational Theory with Short-Range Density-Functional Dynamic Correlation
摘要：
已知多组态波函数可以定性正确地描述玻恩-奥本海默表面上的电子结构。然而，对于定量的反应能，动力学相关性起源于许多涉及激发出受限轨道空间，活性空间，必须加以考虑。标准程序涉及近似，最终限制了最终的精度（最突出的是，多参考扰动理论）。与此同时，由于需要获得更高阶的约化密度矩阵，计算成本急剧增加。正是这种不平衡，使我们在这里提出了一个MC-srDFT-D混合方法的半经典色散（D）的修正，以涵盖长程动力学相关的多组态（MC）波函数理论，其中包括短程（sr）的动力学相关的密度泛函理论（DFT）没有重复计算。我们证明，这种方法的可靠性是非常好的（在可以忽略不计的成本），特别是当考虑到标准的二阶多参考扰动理论通常高估色散相互作用。
英文摘要：
Multi-configurational wave functions are known to describe electronic structure across a Born-Oppenheimer surface qualitatively correct. However, for quantitative reaction energies, dynamical correlation originating from the many configurations involving excitations out of the restricted orbital space, the active space, must be considered. Standard procedures involve approximations that eventually limit the ultimate accuracy achievable (most prominently, multi-reference perturbation theory). At the same time, the computational cost increase dramatically due to the necessity to obtain higher-order reduced density matrices. It is this disproportion that leads us here to propose a MC-srDFT-D hybrid approach of semiclassical dispersion (D) corrections to cover long-range dynamical correlation in a multi-configurational (MC) wave function theory which includes short-range (sr) dynamical correlation by density functional theory (DFT) without double counting. We demonstrate that the reliability of this approach is very good (at negligible cost), especially when considering that standard second-order multi-reference perturbation theory usually overestimates dispersion interactions.
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