论文标题
二阶自一致的场算法：从经典到量子核
Second-order self-consistent field algorithms: from classical to quantum nuclei
论文作者
论文摘要
这项工作提出了一个通用框架，用于通过利用从微分几何形状借用的概念来得出精确和近似牛顿自洽场（SCF）轨道优化算法。在此框架内，我们将增强的Roothaan-hall（ARH）算法扩展到无限制的电子和核电子计算。我们证明，ARH在SCF问题的稳定性和计算成本之间产生了极好的折衷，而SCF问题很难与常规的一阶优化策略相聚。在电子情况下，我们表明ARH通过几个铁硫簇的示例克服了强相关分子中轨道的缓慢收敛性。对于核电子计算，ARH显着增强了针对小分子的收敛性，如一系列质子化水簇所证明的那样。
This work presents a general framework for deriving exact and approximate Newton self-consistent field (SCF) orbital optimization algorithms by leveraging concepts borrowed from differential geometry. Within this framework, we extend the augmented Roothaan--Hall (ARH) algorithm to unrestricted electronic and nuclear-electronic calculations. We demonstrate that ARH yields an excellent compromise between stability and computational cost for SCF problems that are hard to converge with conventional first-order optimization strategies. In the electronic case, we show that ARH overcomes the slow convergence of orbitals in strongly-correlated molecules with the example of several iron-sulfur clusters. For nuclear-electronic calculations, ARH significantly enhances the convergence already for small molecules, as demonstrated for a series of protonated water clusters.
