使用局部振动模式理论对振动斯塔克效应（VSE）探针进行的关键评估。,Sensors

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使用局部振动模式理论对振动斯塔克效应（VSE）探针进行的关键评估。
Sensors ( IF 3.4 ) Pub Date : 2020-04-21 , DOI: 10.3390/s20082358
Niraj Verma ₁ , Yunwen Tao ₁ , Wenli Zou ₂ , Xia Chen ₃ , Xin Chen ₄ , Marek Freindorf ₁ , Elfi Kraka ₁

Affiliation

在过去的二十年中，Stark振动效应已成为使用红外光谱法测量和分析各种化学环境中原位电场强度的重要工具。此效应的基本假设是目标分子的正常拉伸模式（例如报道分子的CO或CN）（称为振动斯塔克效应探针）处于局部状态，并且没有与其他内部坐标的质量耦合，因此其频移直接反映附近电场的影响。但是，这一基本假设的有效性从未得到评估。考虑到正常模式通常由于质量耦合而被散布的事实，因此该分析为时已晚。因此，我们对68种斯塔克振动探针进行了全面评估，并评估了候选探针结合拉伸的正常法向振动与其他内部坐标驱动的局部振动的解耦程度。我们使用的独特工具是Konkoli和Cremer最初引入的局部模式分析，特别是将正常模式分解为局部模式的贡献。根据我们的结果，我们推荐31个具有局部靶标键的多原子分子作为理想的振动斯塔克效应探针候选对象。特别是将正常模式分解为局部模式贡献。根据我们的结果，我们推荐31个具有局部靶标键的多原子分子作为理想的振动斯塔克效应探针候选对象。特别是将正常模式分解为局部模式贡献。根据我们的结果，我们推荐31个具有局部靶标键的多原子分子作为理想的振动斯塔克效应探针候选对象。

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A Critical Evaluation of Vibrational Stark Effect (VSE) Probes with the Local Vibrational Mode Theory.

Over the past two decades, the vibrational Stark effect has become an important tool to measure and analyze the in situ electric field strength in various chemical environments with infrared spectroscopy. The underlying assumption of this effect is that the normal stretching mode of a target bond such as CO or CN of a reporter molecule (termed vibrational Stark effect probe) is localized and free from mass-coupling from other internal coordinates, so that its frequency shift directly reflects the influence of the vicinal electric field. However, the validity of this essential assumption has never been assessed. Given the fact that normal modes are generally delocalized because of mass-coupling, this analysis was overdue. Therefore, we carried out a comprehensive evaluation of 68 vibrational Stark effect probes and candidates to quantify the degree to which their target normal vibration of probe bond stretching is decoupled from local vibrations driven by other internal coordinates. The unique tool we used is the local mode analysis originally introduced by Konkoli and Cremer, in particular the decomposition of normal modes into local mode contributions. Based on our results, we recommend 31 polyatomic molecules with localized target bonds as ideal vibrational Stark effect probe candidates.

更新日期：2020-04-21

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