Tavares Sérgio R, Vaiss Viviane S, Antunes Florence P Novais, Fonseca Carla G, Nangoi Inna M, Moraes Pedro Ivo R, Soares Carla V, Haddad Juliana F S, Lima Larissa L, Silva Bruna N N, Leitão Alexandre A
Group of Physical Chemistry of Solids and Interfaces - GFQSI, Departamento de Química-ICE., Universidade Federal de Juiz de Fora, Juiz de Fora, MG 36036-330, Brazil.
Dalton Trans. 2018 Feb 27;47(9):2852-2866. doi: 10.1039/c7dt03730a.
The intercalated layered materials are commonly built from structures complex enough to have large unit cells and, because of this, calculations of their electronic structures are very demanding in terms of memory, processing and time. Also, the versatility of these compounds enables the synthesis of a large number of derived materials difficult to characterize. Only in the last two decades, a combination of theoretical methodologies and advances in processing made density-functional theory (DFT) calculations quite interesting as an investigation tool for this family of materials. Since the intercalated layered or lamellar compounds correspond to a large group of important classes of materials and their experimental data were, and are still being, generated, only a small part of the data comes from electronic structure simulations. In this review, we have listed some relevant types of intercalated lamellar materials, the useful methodologies implemented in the standard suit of codes for DFT calculations and examples of the many applications of the calculations to the understanding of physical and chemical properties, to the planning of novel materials with desirable properties, and even to assist the structural characterization, by simulating complex results from nuclear magnetic resonance, vibrational spectroscopy and powder X-ray diffraction. In addition to the properties simulated directly as observables, other quantities such as density of states, partial charges and electronic density difference, provide relevant information about the materials and their behavior under diverse physical and chemical conditions. The combination of the geometric, electronic and vibrational structures also leads to the simulations of thermodynamic potentials, entropy and phase diagrams in the solid state. This significant ensemble of research tools makes DFT calculations very compelling and useful to gain new insights into innovation developments for intercalated lamellar materials.
插层层状材料通常由结构复杂到足以拥有大晶胞的结构构成，因此，对其电子结构的计算在内存、处理能力和时间方面要求极高。此外，这些化合物的多功能性使得大量衍生材料的合成变得困难，难以对其进行表征。仅在过去二十年中，理论方法与处理技术的进步相结合，使得密度泛函理论（DFT）计算作为研究这类材料的工具变得相当有趣。由于插层层状或层状化合物对应着一大类重要的材料，并且它们的实验数据过去一直在产生，现在仍在产生，而只有一小部分数据来自电子结构模拟。在本综述中，我们列出了一些相关类型的插层层状材料、DFT计算标准代码套件中实施的有用方法，以及计算在理解物理和化学性质、设计具有理想性质的新型材料甚至辅助结构表征方面的许多应用实例，通过模拟核磁共振、振动光谱和粉末X射线衍射的复杂结果来实现。除了直接作为可观测量模拟的性质外，其他量，如态密度、部分电荷和电子密度差，提供了有关材料及其在不同物理和化学条件下行为的相关信息。几何、电子和振动结构的结合还导致了对固态热力学势、熵和相图的模拟。这一重要的研究工具集合使得DFT计算对于深入了解插层层状材料的创新发展非常有吸引力且有用。
