Using projection operators with maximum overlap methods to simplify challenging self-consistent field optimization,Journal of Computational Chemistry

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Using projection operators with maximum overlap methods to simplify challenging self-consistent field optimization
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2021-12-22 , DOI: 10.1002/jcc.26797
Hector H Corzo ₁ , Ali Abou Taka ₁ , Aurora Pribram-Jones ₁ , Hrant P Hratchian ₁

Affiliation

Maximum overlap methods are effective tools for optimizing challenging ground- and excited-state wave functions using self-consistent field models such as Hartree-Fock and Kohn-Sham density functional theory. Nevertheless, such models have shown significant sensitivity to the user-defined initial guess of the target wave function. In this work, a projection operator framework is defined and used to provide a metric for non-aufbau orbital selection in maximum-overlap-methods. The resulting algorithms, termed the Projection-based Maximum Overlap Method (PMOM) and Projection-based Initial Maximum Overlap Method (PIMOM), are shown to perform exceptionally well when using simple user-defined target solutions based on occupied/virtual molecular orbital permutations. This work also presents a new metric that provides a simple and conceptually convenient measure of agreement between the desired target and the current or final SCF results during a calculation employing a maximum-overlap method.

中文翻译：

使用具有最大重叠方法的投影算子来简化具有挑战性的自洽场优化

最大重叠方法是使用自洽场模型（例如 Hartree-Fock 和 Kohn-Sham 密度泛函理论）优化具有挑战性的基态和激发态波函数的有效工具。然而，这些模型对用户定义的目标波函数的初始猜测显示出显着的敏感性。在这项工作中，定义了一个投影算子框架，并用于为最大重叠方法中的非 aufbau 轨道选择提供度量。由此产生的算法，称为基于投影的最大重叠方法 (PMOM) 和基于投影的初始最大重叠方法 (PIMOM)，在使用基于占据/虚拟分子轨道排列的简单用户定义目标解决方案时表现出异常出色的性能。

更新日期：2022-01-20

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