The necessity of periodic boundary conditions for the accurate calculation of crystalline terahertz spectra
The necessity of periodic boundary conditions for the accurate calculation of crystalline terahertz spectra
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DOI：
10.1039/d1cp02496e
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发表时间：
2021-09-08
影响因子：
3.3
通讯作者：
Ruggiero, Michael T.
中科院分区：
文献类型：
--
作者：
Banks, Peter A.;Burgess, Luke;Ruggiero, Michael T.
太赫兹振动光谱学已经成为一种强大的光谱技术，它提供了关于固体中发生的远程相互作用以及相关的集体动力学的有价值的信息。然而，太赫兹科学还相对较新，在过去的几十年里已经取得了重大进展，对实验太赫兹光谱的解释和分配产生了深远的影响。具体地说，因为不存在任何官能团或特定材料的太赫兹跃迁，所以如果没有额外的分析，特别是计算模拟，就不可能解释实验光谱。多年来，使用周期性边界条件的模拟已被证明在再现实验太赫兹动力学方面最成功，这是因为计算能够准确地考虑长程力。另一方面，文献中有许多利用气相团簇几何结构的报告，取得了不同程度的明显成功。这一观点将简要介绍太赫兹科学，特别是太赫兹光谱学，然后评估气相和周期性模拟晶体太赫兹光谱的分配，突出潜在的陷阱和未来努力的良好做法。
Terahertz vibrational spectroscopy has emerged as a powerful spectroscopic technique, providing valuable information regarding long-range interactions - and associated collective dynamics - occurring in solids. However, the terahertz sciences are relatively nascent, and there have been significant advances over the last several decades that have profoundly influenced the interpretation and assignment of experimental terahertz spectra. Specifically, because there do not exist any functional group or material-specific terahertz transitions, it is not possible to interpret experimental spectra without additional analysis, specifically, computational simulations. Over the years simulations utilizing periodic boundary conditions have proven to be most successful for reproducing experimental terahertz dynamics, due to the ability of the calculations to accurately take long-range forces into account. On the other hand, there are numerous reports in the literature that utilize gas phase cluster geometries, to varying levels of apparent success. This perspective will provide a concise introduction into the terahertz sciences, specifically terahertz spectroscopy, followed by an evaluation of gas phase and periodic simulations for the assignment of crystalline terahertz spectra, highlighting potential pitfalls and good practice for future endeavors.