The Local Vibrational Mode Theory and Its Place in the Vibrational Spectroscopy Arena
The Local Vibrational Mode Theory and Its Place in the Vibrational Spectroscopy Arena
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DOI：
10.1021/acs.jpca.2c05962
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发表时间：
2022-11-08
影响因子：
2.9
通讯作者：
Freindorf，Marek
中科院分区：
文献类型：
--
作者：
Kraka，Elfi;Quintano，Mateus;Freindorf，Marek
这篇专题文章首先重点介绍了红外和拉曼光谱领域的一些最新实验和理论进展，让我们了解了这个奋斗领域的广度和动态。然后回顾局部模态理论，展示局部振动模态是如何从基本简正模态导出的。引入的新功能补充了当前的理论工作：（i）基于局部模式力常数的独特键强度测量，范围从不同环境中的单分子键合到周期系统和晶体中的键合，以及（ii）通过精确定位和探测特定键拉伸对正常模式的贡献之间的相互作用来解释振动光谱的新方法。所有这些都代表了一种解决正常模式本质的方法，即多原子分子中的振动运动是离域的。报告了局部模式分析的三个当前焦点，展示了局部模式分析如何提取隐藏在支持当前实验的振动光谱数据中的重要信息：（i）血红素蛋白中的金属-配体键合，例如肌红蛋白和神经红蛋白； (ii) DNA正常模式的解缠结； (iii) 水簇和冰中的氢键。最后，对其他研究组对局部模态分析的使用进行了总结。我们的愿景是，未来局部模式分析将被社区常规应用，并且这篇专题文章将成为未来实验与理论之间合作的孵化器。
This Feature Article starts highlighting some recent experimental and theoretical advances in the field of IR and Raman spectroscopy, giving a taste of the breadth and dynamics of this striving field. The local mode theory is then reviewed, showing how local vibrational modes are derived from fundamental normal modes. New features are introduced that add to current theoretical efforts: (i) a unique measure of bond strength based on local mode force constants ranging from bonding in single molecules in different environments to bonding in periodic systems and crystals and (ii) a new way to interpret vibrational spectra by pinpointing and probing interactions between particular bond stretching contributions to the normal modes. All of this represents a means to work around the very nature of normal modes, namely that the vibrational motions in polyatomic molecules are delocalized. Three current focus points of the local mode analysis are reported, demonstrating how the local mode analysis extracts important information hidden in vibrational spectroscopy data supporting current experiments: (i) metal–ligand bonding in heme proteins, such as myoglobin and neuroglobin; (ii) disentanglement of DNA normal modes; and (iii) hydrogen bonding in water clusters and ice. Finally, the use of the local mode analysis by other research groups is summarized. Our vision is that in the future local mode analysis will be routinely applied by the community and that this Feature Article serves as an incubator for future collaborations between experiment and theory.