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探索 (n - 1) d亚价相关性和自旋轨道合对素结合的影响

Nisha Mehta¹, Jan M L Martin¹

¹Department of Molecular Chemistry and Materials Science, Weizmann Institute of Science, 7610001 Rehovot, Israel. nisha.mehta@weizmann.ac.il.

Physical chemistry chemical physics : PCCP

|August 13, 2024

概括

这项研究表明,内部外电子相关性显著影响了素结合,而 (n-1) d相关性起到了主导作用,与素结合不同. 此外,还分析了旋转轨道合效应.

科学领域:

计算化学是一种计算化学.
量子化学是一种量子化学.
非共价相互作用非共价相互作用

背景情况:

素结合是化学和生物学中的一个关键的非共价相互作用.
了解控制这些相互作用的电子因素对于预测分子行为至关重要.
之前关于素结合的研究显示了不同的电子相关性效应.

研究的目的:

通过计算来研究亚价电子相关的作用,特别是 (n-1) d和 (n-1) sp,在素结合中.
为了将这些效应与素结合中观察到的效应进行比较.
分析二次旋转轨道合 (SOC2) 对素键能量的影响.

主要方法:

高级量子化学计算,包括PNO-LCCSD (T) 和DF-CCSD.
对相互作用能量组件的分析,重点是PNO-LMP2或DF-MP2的贡献.
包括二次旋转轨道合 (SOC2) 效应.

主要成果:

内 (n-1) d相关性降低了素结合中的相互作用能量,与素结合的发现形成鲜明对比.
(n-1) sp亚价相关性具有较小,数量级较低的影响.
(n-1) d相关成分 (PNO-LMP2或DF-MP2) 是相互作用能量的主要贡献者.

结论:

内 (n-1) d电子相关性是素结合的一个关键因素,与素结合相比,它具有明显的效果.
SOC2效应比 (n-1) d相关性不那么显著,但不算小事,特别是在 (Te) 和 (Se) 复合体中.
SOC2通常比二聚体更能稳定单体,减少结合,其对复杂稳定性的影响因几何学而异.

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