Exploring the Forces Contributing to Noncovalent Bonding by Microwave Spectroscopy and Structural Characterization of Gas-Phase Heterodimers of Protic Acids with Haloethylenes
Exploring the Forces Contributing to Noncovalent Bonding by Microwave Spectroscopy and Structural Characterization of Gas-Phase Heterodimers of Protic Acids with Haloethylenes
复制标题
通过微波光谱和质子酸与卤代乙烯气相异二聚体的结构表征探索促成非共价键合的力
DOI：
10.1021/acs.jpca.9b07960
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Marshall, Mark D.
中科院分区：
文献类型：
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作者：
Leung, Helen O.;Marshall, Mark D.
通过微波旋转光谱在质子酸卤代乙烯异二聚体的系统研究中获得的结构参数的详细比较被用来调查有助于分子间相互作用的力量。使用结构数据和化学直觉得到的结论补充了从量子化学计算中获得的信息，以完善对复合物形成的各种贡献的理解。所观察到的结构，代表的全球最小的势能表面上，被发现反映最佳静电和空间要求之间的平衡，或者换句话说，如何以及两个相互作用的分子配合在一起。结构的趋势是合理的，在熟悉的化学概念的亲电性或亲核性的相互作用位点的调制吸电子和供电子基团沿着与两个分子之间的最佳相互作用的几何要求。
A detailed comparison of structural parameters obtained via microwave rotational spectroscopy in a systematic study of protic acid-haloethylene heterodimers is used to investigate the forces contributing to intermolecular interactions. Conclusions reached using structural data and chemical intuition are supplemented with information obtained from quantum-chemistry calculations to refine the understanding of the various contributions to complex formation. The observed structures, representative of the global minimum on the potential energy surface, are found to reflect a balance between optimal electrostatics and steric requirements, or in other words, how well the two interacting molecules fit together. Structural trends are rationalized in terms of familiar chemical concepts of the electrophilicity or nucleophilicity of interaction sites as modulated by electron-withdrawing and electron-donating groups along with the geometric requirements for optimal interactions between the two molecules.