DFT calculations for structural prediction and applications of intercalated lamellar compounds

Abstract

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.

A computational study of the properties of low- and high-index Pd, Cu and Zn surfaces

“…Computer simulation and computer-assisted design provide a powerful approach for understanding and optimizing functional materials; 1,2 and detailed knowledge of surface properties is necessary in understanding the applied chemistry, including catalytic behaviour, of materials. A particularly important quantity is the surface energy, 3 which is crucial in determining surface structure, including for nanoparticulate systems with high surface areas or non-crystalline cores.…”

Structural and Electronic Properties of Iron-Doped Sodium Montmorillonite Clays: A First-Principles DFT Study

“…Computational simulations provide a powerful tool to determine the most probable positions of the cations in the lamellae, as well as the number of cations in the interlamellar domain. Tavares et al and Costa et al, using ab initio density functional theory (DFT) calculations with periodic boundary conditions, were able to accurately predict crystallographic and electronic properties of clays such as double lamellar hydroxides. , There are several theoretical studies that analyze the hydration of ions confined in the interlayer space of montmorillonites, − investigations that involve the interaction of organic components which exploit the adsorptive properties of Mt − for application as adsorbent of pollutants, and other medical applications.…”

One molecule, two states: Single molecular switch on metallic electrodes

“…Both classes of vdW methods are efficient to treat long‐range electron dispersive correlation problems, and for which very encouraging developments have been achieved recently. For more detailed developments of the DFT methods, we would recommend the recently published comprehensive and insightful review articles in References 53–57. Here we briefly introduce three most popular approaches that are normally employed for the design of molecular switches.…”