Second-Order Self-Consistent Field Algorithms: From Classical to Quantum Nuclei
Second-Order Self-Consistent Field Algorithms: From Classical to Quantum Nuclei
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DOI：
10.1021/acs.jctc.2c01035
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发表时间：
2023-02-14
影响因子：
5.5
通讯作者：
Reiher, Markus
中科院分区：
文献类型：
--
作者：
Feldmann, Robin;Baiardi, Alberto;Reiher, Markus
这项工作提出了一个通用的框架，推导精确和近似牛顿自洽场（SCF）轨道优化算法，利用从微分几何借用的概念。在这个框架内，我们扩展了增强Roothaan-Hall（ARH）算法，不受限制的电子和核电子计算。我们表明，ARH产生了一个很好的折衷稳定性和计算成本的SCF问题，难以收敛与传统的一阶优化策略。在电子的情况下，我们表明，ARH克服了轨道的收敛速度慢，在强相关的分子与几个铁硫簇的例子。对于核电子计算，ARH显着提高收敛已经为小分子，如一系列质子化的水簇。
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.