Tristan H. Borchers, Filip Topić, Mihails Arhangelskis, Michael Ferguson, Cameron B. Lennox, Patrick A. Julien, Tomislav Friščić
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引用次数: 0
Abstract
Low-frequency Raman, also known as terahertz-Raman (THz-Raman), spectroscopy offers a laboratory benchtop-based alternative to synchrotron X-ray diffraction for real-time, in situ monitoring of ball-milling mechanochemical reactions. Although direct monitoring of the long-range structure of materials during mechanochemical reactions is generally challenging by conventional Raman spectroscopy, and typically requires synchrotron X-ray diffraction, here we use THz-Raman spectroscopy to monitor mechanosynthesis of cocrystals, stoichiomorphs, and polymorphs, detect multi-step sequences, and discover solid-state phases in systems difficult to differentiate using fingerprint-region Raman spectroscopy—all through real-time observation of changes in lattice vibrational models. The methodology is augmented by periodic density functional theory (DFT), which enables structural interpretation of spectroscopic changes, notably the identification of THz-Raman bands associated with halogen bond transformations. Simultaneous monitoring of mechanochemical processes in both the fingerprint and low-frequency Raman regions enables real-time observation of changes to extended as well as molecular structure during milling, in a single laboratory benchtop experiment, without synchrotron radiation.
低频拉曼(又称太赫兹-拉曼,THz-Raman)光谱法为实验室台式同步辐射 X 射线衍射法提供了一种替代方法,可用于实时、原位监测球磨机械化学反应。虽然在机械化学反应过程中直接监测材料的长程结构通常是传统拉曼光谱法所无法实现的,而且通常需要同步辐射 X 射线衍射法,但在这里,我们使用太赫兹-拉曼光谱法监测共晶体、共晶和多晶体的机械合成,检测多步序列,并在使用指纹区拉曼光谱法难以区分的系统中发现固态相--所有这些都是通过实时观测晶格振动模型的变化实现的。周期性密度泛函理论(DFT)对该方法进行了增强,从而能够对光谱变化进行结构解释,特别是识别与卤素键转化相关的太赫兹-拉曼带。同时监测指纹区和低频拉曼区的机械化学过程,可在实验室台式实验中实时观察研磨过程中扩展分子结构的变化,而无需同步辐射。
期刊介绍:
Chem, affiliated with Cell as its sister journal, serves as a platform for groundbreaking research and illustrates how fundamental inquiries in chemistry and its related fields can contribute to addressing future global challenges. It was established in 2016, and is currently edited by Robert Eagling.