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Tipping the Scales: Spectroscopic Tools for Intermolecular Energy Balances
The Journal of Physical Chemistry Letters ( IF 5.7 ) Pub Date : 2017-11-08 00:00:00 , DOI: 10.1021/acs.jpclett.7b02337
Anja Poblotzki 1 , Hannes C. Gottschalk 1 , Martin A. Suhm 1
Affiliation  

Intermolecular energy balances are supramolecular complexes with a nearly degenerate bistable docking structure and low barriers in between, which can be tuned by chemical substitution to prefer one or the other site. The docking preference can be probed by forming the complexes in a supersonic jet expansion and by measuring their spectroscopic signature. Linear spectroscopies are shown to be well suited for this purpose, in particular when they are assisted by more sensitive techniques and by approximate computed photon interaction cross sections. Molecular analogues of conventional beam balances, seesaw balances, and torsional balances are discussed, all based on noncovalent interactions. The discrimination of energy differences down to the sub-kJ/mol level is demonstrated. The correspondence to intramolecular torsional balances in NMR spectroscopy is outlined. Besides highlighting conformational preferences, the results of intermolecular balance experiments can serve as critical benchmarks for an accurate description of intermolecular forces and zero-point vibrational energies.

中文翻译:

缩小尺度:分子间能量平衡的光谱工具

分子间能量平衡是具有几乎简并的双稳态对接结构且其间的低势垒的超分子复合物,可以通过化学取代来调节其以偏爱一个或另一个位点。可以通过在超音速射流扩展中形成复合物并测量其光谱特征来探究对接偏好。线性光谱表明非常适合此目的,尤其是在借助更灵敏的技术和近似计算的光子相互作用横截面的辅助下。讨论了常规束天平,跷跷板天平和扭转天平的分子类似物,所有这些均基于非共价相互作用。证明了对低至亚千焦耳/摩尔水平的能量差异的辨别。概述了在NMR光谱中与分子内扭转平衡的对应关系。除了突出构象偏好之外,分子间平衡实验的结果还可以作为准确描述分子间力和零点振动能的关键基准。
更新日期:2017-11-08
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