区分 Stark 探针中的静电效应和显式离子相互作用,The Journal of Physical Chemistry B

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区分 Stark 探针中的静电效应和显式离子相互作用
The Journal of Physical Chemistry B ( IF 2.8 ) Pub Date : 2023-03-14 , DOI: 10.1021/acs.jpcb.2c08030
Anwesha Maitra ₁ , Pratyusha Das ₁ , Barry C Thompson ₁ , Jahan M Dawlaty ₁

Affiliation

振动 Stark 探头是用于测量各种化学环境中局部电场的敏锐工具。由于探针的特定相互作用，例如氢键和路易斯键，频移的解释通常变得复杂。因此，区分纯静电响应和由于此类特定相互作用而产生的响应很重要。在这里，我们报告了一个分子系统，它对单个离子的斯塔克效应和离子与探针的显式路易斯键合都很敏感。该分子由冠醚和附加的苯甲腈组成。皇冠捕获各种电荷的阳离子，并且来自离子的电场被苯甲腈探针感测。此外，孤对的苄腈可以通过向离子提供部分电荷密度来与某些离子进行路易斯相互作用。我们的系统表现出这两种效应，因此是区分纯静电和路易斯相互作用的合适试验台。我们的计算结果表明，离子的静电影响在远距离有效，而路易斯相互作用仅在允许轨道重叠的距离内变得重要。我们的结果可能有助于使用腈探针测量复杂离子环境（如电极-电解质界面）中的静电和配位效应。我们的系统表现出这两种效应，因此是区分纯静电和路易斯相互作用的合适试验台。我们的计算结果表明，离子的静电影响在远距离有效，而路易斯相互作用仅在允许轨道重叠的距离内变得重要。我们的结果可能有助于使用腈探针测量复杂离子环境（如电极-电解质界面）中的静电和配位效应。我们的系统表现出这两种效应，因此是区分纯静电和路易斯相互作用的合适试验台。我们的计算结果表明，离子的静电影响在远距离有效，而路易斯相互作用仅在允许轨道重叠的距离内变得重要。我们的结果可能有助于使用腈探针测量复杂离子环境（如电极-电解质界面）中的静电和配位效应。

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Distinguishing between the Electrostatic Effects and Explicit Ion Interactions in a Stark Probe

Vibrational Stark probes are incisive tools for measuring local electric fields in a wide range of chemical environments. The interpretation of the frequency shift often gets complicated due to the specific interactions of the probe, such as hydrogen bonding and Lewis bonding. Therefore, it is important to distinguish between the pure electrostatic response and the response due to such specific interactions. Here we report a molecular system that is sensitive to both the Stark effect from a single ion and the explicit Lewis bonding of ions with the probe. The molecule consists of a crown ether with an appended benzonitrile. The crown captures cations of various charges, and the electric field from the ions is sensed by the benzonitrile probe. Additionally, the lone pair of the benzonitrile can engage in Lewis interactions with some of the ions by donating partial charge density to the ions. Our system exhibits both of these effects and therefore is a suitable test bed for distinguishing between the pure electrostatic and the Lewis interactions. Our computational results show that the electrostatic influence of the ion is operative at large distances, while the Lewis interaction becomes important only within distances that permit orbital overlap. Our results may be useful for using the nitrile probe for measuring electrostatic and coordination effects in complex ionic environments such as the electrode–electrolyte interfaces.

更新日期：2023-03-14

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