The axiomatic approach to chemical concepts
The axiomatic approach to chemical concepts
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DOI：
10.1016/j.comptc.2018.09.006
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发表时间：
2018-10-15
影响因子：
2.8
通讯作者：
Heidar-Zadeh, Farnaz
中科院分区：
文献类型：
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作者：
Ayers, Paul W.;Fias, Stijn;Heidar-Zadeh, Farnaz
许多化学语言和思想的核心概念来自化学家丰富的历史经验，无法从基础物理学中精确定义。在这种情况下，采取公理化的方法是有用的：列出人们希望一个概念拥有的化学、数学和计算性质，然后找到满足这些要求的概念的严格（如果可能的话，优雅）数学公式。如果这个数学公式依赖于基本量-量子力学可观测量、约化密度矩阵或N电子波函数-而不是依赖于方法的量（例如，轨道），其对于分子电子结构问题的某些计算方法没有定义。这就确保了对化学直觉的追求不会使人们远离潜在的物理学。它还确保人们可以解释任何计算方法的结果，甚至方法（例如，量子蒙特卡罗），不涉及任何分子轨道或价键模型。
Many concepts that are central to chemical language and thought emerge from the wealth of chemists' historical experience and cannot be precisely defined mathematically from the underlying physics. In such cases, it is useful to take an axiomatic approach: list the chemical, mathematical and computational properties that one desires for a concept to possess, and then find the rigorous (and, if possible, elegant) mathematical formulation of the concept that satisfies those desiderata. This mathematical formulation is most useful if it relies on fundamental quantities-quantum-mechanical observables, reduced density matrices, or the N-electron wavefunction-rather than method-dependent quantities (e.g., orbitals) that are not defined for some computational approaches to the molecular electronic structure problem. This ensures that the pursuit of chemical intuition does not lead one too far from the underlying physics. It also ensures that one can interpret the results of any computational method, even methods (e.g., quantum Monte Carlo) that make no reference to any molecular-orbital or valence-bond model.