态、构型和轨道的正交性

IF 1.8 3区 化学 Q1 HISTORY & PHILOSOPHY OF SCIENCE Foundations of Chemistry Pub Date : 2022-02-02 DOI:10.1007/s10698-022-09417-y
Balakrishnan Viswanathan, Mohamed Shajahan Gulam Razul
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引用次数: 0

摘要

本文探讨了态相互正交性质下的构型和轨道的正交性约束。正交性约束导致影响化学系统描述的性质。当状态被描述为(正交或非正交)构型的线性组合时,系数矩阵(将构型映射到状态)对角化S−1H。因此,单构型态只可能存在于单电子系统中:非正交构型只有在S−1H是对角的情况下才会产生单构型态,但这将违反标准正交化约束。此外,系数矩阵不被约束为平方(构型的数量可能与构型的数量不同)。同样,用于构造构型的轨道也可以是正交的或非正交的;轨道只要求在单电子极限下相互正交。由于其数学和概念上的简单性,正交轨道通常是首选,导致虚构的未占据轨道。由于Fock算子是正交不可知的,因此可以通过对每个电子独立求解Fock方程来生成非正交(已占)轨道;由这个概念产生的虚轨道是真激发轨道,因为它们是Fock算子的本征解。此外,我们还表明,生成的分子轨道的数量并不局限于计算中使用的原子轨道(或基函数)的数量。本文探讨了在各种正交状态下需要满足的数学关系。我们还提出了数学关系,提供的结果是独立于正交近似在一个特定的计算方法。
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Orthogonality properties of states, configurations, and orbitals

This manuscript explores the orthogonality constraints on configurations and orbitals subject to the property that states are mutually orthogonal. The orthogonality constraints lead to properties that affect the description of chemical systems. When states are described as linear combinations of (orthogonal or non-orthogonal) configurations, the coefficient matrix (mapping configurations to states) diagonalises S−1H. Therefore, single-configuration states are only possible in one-electron systems: non-orthogonal configurations yield single-configuration states only if S−1H is diagonal, but this would violate the orthonormalisation constraint. Further, the coefficient matrix is not constrained to be square (the number of configurations may differ from the number of configurations). Similarly, the orbitals used to construct configurations may also be orthogonal or non-orthogonal; orbitals are only required to be mutually orthogonal at the one-electron limit. Orthogonal orbitals are generally preferred due to their mathematical and conceptual simplicity, leading to fictitious unoccupied orbitals. Since the Fock operator is orthogonality agnostic, non-orthogonal (occupied) orbitals can be generated by solving the Fock equation independently for each electron; the virtual orbitals produced by this conception are true excitation orbitals as they are eigensolutions of the Fock operator. Additionally, we show that the number of molecular orbitals generated is not restricted to the number of atomic orbitals (or basis functions) employed in the computation. This manuscript explores the mathematical relationships that need to be satisfied under the various orthogonality regimes. We also present mathematical relationships that provide results that are independent of the orthogonality approximation within a particular computational method.

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Foundations of Chemistry
Foundations of Chemistry HISTORY & PHILOSOPHY OF SCIENCE-
自引率
22.20%
发文量
35
期刊介绍: Foundations of Chemistry is an international journal which seeks to provide an interdisciplinary forum where chemists, biochemists, philosophers, historians, educators and sociologists with an interest in foundational issues can discuss conceptual and fundamental issues which relate to the `central science'' of chemistry. Such issues include the autonomous role of chemistry between physics and biology and the question of the reduction of chemistry to quantum mechanics. The journal will publish peer-reviewed academic articles on a wide range of subdisciplines, among others: chemical models, chemical language, metaphors, and theoretical terms; chemical evolution and artificial self-replication; industrial application, environmental concern, and the social and ethical aspects of chemistry''s professionalism; the nature of modeling and the role of instrumentation in chemistry; institutional studies and the nature of explanation in the chemical sciences; theoretical chemistry, molecular structure and chaos; the issue of realism; molecular biology, bio-inorganic chemistry; historical studies on ancient chemistry, medieval chemistry and alchemy; philosophical and historical articles; and material of a didactic nature relating to all topics in the chemical sciences. Foundations of Chemistry plans to feature special issues devoted to particular themes, and will contain book reviews and discussion notes. Audience: chemists, biochemists, philosophers, historians, chemical educators, sociologists, and other scientists with an interest in the foundational issues of science.
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