Tecmer Paweł, Boguslawski Katharina
Institute of Physics, Faculty of Physics, Astronomy, and Informatics, Nicolaus Copernicus University in Toruń, Grudziądzka 5, 87-100 Toruń, Poland.
Phys Chem Chem Phys. 2022 Oct 5;24(38):23026-23048. doi: 10.1039/d2cp02528k.
In this review, we discuss the recent progress in developing geminal-based theories for challenging problems in quantum chemistry. Specifically, we focus on the antisymmetrized geminal power, generalized valence bond, antisymmetrized product of strongly orthogonal geminals, singlet-type orthogonal geminals, the antisymmetric product of 1-reference orbital geminal, also known as the pair coupled cluster doubles ansatz, and geminals constructed from Richardson-Gaudin states. Furthermore, we review various corrections to account for the missing dynamical correlation effects in geminal models and possible extensions to target electronically excited states and open-shell species. Finally, we discuss some numerical examples and present-day challenges for geminal-based models, including a quantitative and qualitative analysis of wave functions, and software availability.
在本综述中，我们讨论了为解决量子化学中的挑战性问题而发展基于双电子对理论的最新进展。具体而言，我们关注反对称双电子对幂、广义价键、强正交双电子对的反对称积、单重态型正交双电子对、单参考轨道双电子对的反对称积（也称为对耦合簇双激发近似）以及由理查森 - 高丁态构建的双电子对。此外，我们回顾了各种修正，以考虑双电子对模型中缺失的动态相关效应，以及针对电子激发态和开壳层物种的可能扩展。最后，我们讨论了一些数值示例以及基于双电子对模型当前面临的挑战，包括波函数的定量和定性分析以及软件可用性。
