向geminal基础的转换及其精确波函数的静止条件

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of Chemical Research Pub Date : 2024-06-18 DOI:10.1007/s00214-024-03131-y
Lasse Kragh Sørensen
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引用次数: 0

摘要

我们展示了从单粒子基到geminal基的变换、不同geminal基之间的变换以及geminal基的李代数。从基变换中,我们可以在基上表达波函数和哈密顿。在geminal基中展开精确波函数的必要条件和充分条件被证明是geminals的布里渊定理。我们还讨论了反不对称geminal幂(AGP)、反不对称geminal乘积(APG)和全geminal乘积(FGP)波函数ansätze中geminals的变分优化。我们表明,使用宝石置换算子来描述宝石旋转会引入主旋转和次旋转。由于geminal的复合玻色子性质,二次旋转会同时旋转参考中的两个geminal。由于 FGP 的完备性,即所有可能的 geminal 组合都存在,FGP 是精确的。FGP中的参数数量与粒子数量成指数关系,就像全构型相互作用(FCI)一样。由于 FGP 中的参考函数既可以是 AGP 波函数,也可以是 APG 波函数,因此在 FGP 扩展中进行截断可以紧凑地表示波函数。
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Transformation to a geminal basis and stationary conditions for the exact wave function therein

We show the transformation from a one-particle basis to a geminal basis, transformations between different geminal bases demonstrate the Lie algebra of a geminal basis. From the basis transformations, we express both the wave function and Hamiltonian in the geminal basis. The necessary and sufficient conditions of the exact wave function expanded in a geminal basis are shown to be a Brillouin theorem of geminals. The variational optimization of the geminals in the antisymmetrized geminal power (AGP), antisymmetrized product of geminals (APG) and the full geminal product (FGP) wave function ansätze are discussed. We show that using a geminal replacement operator to describe geminal rotations introduce both primary and secondary rotations. The secondary rotations rotate two geminals in the reference at the same time due to the composite boson nature of geminals. Due to the completeness of the FGP, where all possible geminal combinations are present, the FGP is exact. The number of parameters in the FGP scale exponentially with the number of particles, like the full configuration interaction (FCI). Truncation in the FGP expansion can give compact representations of the wave function since the reference function in the FGP can be either the AGP or APG wave function.

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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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