V2EX static correlation

Static Correlation

Definition / 定义

静态相关(static correlation):量子化学/电子结构理论中的术语,指在某些分子或状态下,仅用一个单一电子组态(单一参考,如单一Slater行列式)无法正确描述体系,必须把多个近简并(能量接近)的电子组态同时纳入,才能得到合理的键合、能量与电子分布。常见于化学键断裂过程、开壳层体系、激发态、过渡金属配合物等情形。
(注:与之相对的常见概念是 dynamic correlation “动态相关”。)

Pronunciation / 发音

/sttk krlen/

Examples / 例句

Static correlation becomes important when a bond is stretched.
当化学键被拉长时,静态相关就会变得重要。

To describe the dissociation of H correctly, the wavefunction must include more than one configuration, reflecting strong static correlation.
要正确描述氢分子(H)的解离,波函数必须包含不止一种电子组态,这体现了强烈的静态相关。

Etymology / 词源

static 源自希腊语 statikos,有“使之站立/静止”的含义;correltion 来自拉丁语 correlatio,意为“相互关系”。在电子结构语境里,“static(静态)”强调这种相关主要来自多个近简并组态的“结构性/基态性质”需要,而不是来自电子瞬时回避造成的“动态”效应。

Related Words / 相关词

Literary Works / 文学作品

  • Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory(Szabo & Ostlund)
  • Molecular Electronic-Structure Theory(Helgaker, Jrgensen & Olsen)
  • A Chemist’s Guide to Density Functional Theory(Koch & Holthausen)
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