We report extensive computational studies of some novel intermolecular systems and their properties. Recombination of alkali‐halide counterions separated by a noncovalently trapped hydrocarbon molecule is prevented by significant potential energy barriers, resulting in unusual metastable insertion complexes. These systems are extremely polar, while the inserted molecule is strongly counter‐polarized, leading to significant cooperative nonadditivity effects. The compression and electric field produced by the counterions favours isomerization of the trapped molecule via a significant reduction of the barriers to bond rearrangement, in a field‐induced mechanochemical process. The predicted IR intensity spectra clearly reflect (1) formation of the insertion complex, rather than simple attachment of alkali halide, and (2) isomerization of the trapped molecule, thus allowing experimental access to these events.

中文翻译：

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抗衡离子捕获分子：从高极性和丰富的红外光谱到诱导的异构化

我们报告了一些新颖的分子间系统及其性能的广泛的计算研究。显着的势能垒可防止被非共价捕获的碳氢化合物分子分隔的碱金属卤化物抗衡离子的重组，从而导致异常的亚稳插入配合物。这些系统是极端极性的，而插入的分子是强烈反极化的，从而导致明显的协同非加性效应。在电场诱导的机械化学过程中，抗衡离子产生的压缩和电场通过显着减少键重排的障碍，有利于捕获分子的异构化。预测的IR强度光谱清楚地反映了（1）插入配合物的形成，而不是碱金属卤化物的简单附着，