First-principles calculations of the stibnite at the level of modified Becke–Johnson exchange potential

The demand for cheaper, nontoxic and earth-abundant materials as absorbing layer for solar cell is immensely needed to replace scarce, toxic and expensive one. In this regard, chalcogenide materials have considerably attracted the attention of a lot of researchers because of showing a great potential for different applications. Stibnite (Sb₂S₃), a chalcogenide binary material is considerably investigated for exploiting its potential for different energy technologies being a less toxic, abundantly available, stable and efficient, which are the fundamentals for sustainability as well as to realize the dream of green energy. In this study, theoretical calculations of the structural, electronic and optical properties of stibnite (Sb₂S₃) crystal structure are presented using the full potential (FP) linearized augmented plane wave (LAPW) framed within density functional theory (DFT). To incorporate the exchange-correlation part in the total energy functional, besides the local density approximation (LDA), Wu-Cohen parameterized generalized gradient approximation (WC-GGA), Perdew–Burke–Ernzerhof parameterized generalized gradient approximation (PBE-GGA), and Perdew–Burke–Ernzerhof generalized gradient approximation for solids and surfaces (PBEsol-GGA) are used for the calculations of the structural parameters, where the Trans-Blaha approach of the modified Becke–Johnson (TB-mBJ) potential is used to get more reliable results for the fundamental band gap energy value. These calculations are performed by involving spin-orbit coupling (SOC) contribution. Additionally, optical properties, such as imaginary and real parts of the dielectric function, optical conductivity, absorption coefficient, refractive index, reflectivity, and electron energy loss function are analyzed. Our first-principles calculations show that Wu-Cohen GGA (WC-GGA) reproduces results for lattice parameters comparable to the experimental measurements. The obtained results of the band gap energy and optical properties with TB-mBJ potential are also closer to the experimental data and, endorse its potentiality for the photovoltaics applications.     

Noble Metal Clusters: Applications in Energy,Environment, and Biology

Sub‐nanometer‐sized metal clusters, having dimensions between metal atoms and nanoparticles, have attracted tremendous attention in the recent past due to their unique physical and chemical properties. As properties of such materials depend strongly on size, development of synthetic routes that allows precise tuning of the cluster cores with high monodispersity and purity is an area of intense research. Such materials are also interesting owing to their wide variety of applications. Novel sensing strategies based on these materials are emerging. Owing to their extremely small size, low toxicity, and biocompatibility, they are widely studied for biomedical applications. Primary focus of this review is to provide an account of the recent advances in their applications in areas such as environment, energy, and biology. With further experimental and theoretical advances aimed at understanding their novel properties and solving challenges in their synthesis, an almost unlimited field of applications can be foreseen.     

Electron emission from diamondoids: a diffusion quantum Monte Carlo study

We present density-functional theory (DFT) and quantum Monte Carlo (QMC) calculations designed to resolve experimental and theoretical controversies over the optical properties of H-terminated C nanoparticles (diamondoids). The QMC results follow the trends of well-converged plane-wave DFT calculations for the size dependence of the optical gap, but they predict gaps that are 1-2 eV higher. They confirm that quantum confinement effects disappear in diamondoids larger than 1 nm, which have gaps below that of bulk diamond. Our QMC calculations predict a small exciton binding energy and a negative electron affinity (NEA) for diamondoids up to 1 nm, resulting from the delocalized nature of the lowest unoccupied molecular orbital. The NEA suggests a range of possible applications of diamondoids as low-voltage electron emitters.     

Quantum mechanics and mechanical properties: Towards twenty-first century materials

The use of materials with otherwise attractive properties is often limited by unacceptable mechanical performance. Fortunately, modern processing techniques are sometimes able to overcome such deficiencies, though a systematic and fundamental approach to materials development has yet to be devised. Recent advances in quantum-mechanical computational capabilities have fostered a growing number of applications that bear directly upon the mechanical properties of materials. After a brief discussion of the role of defect structures in mediating deformation behaviour, techniques for computing properties of solids within a quantum-mechanical framework are reviewed. Examples are cited where insight into macroscopic behaviour has been attained from the application of quantum-mechanical calculations to materials of technological importance.     

并苯纳米环[6]CA及其衍生物的电子结构和光物理性质的密度泛函理论研究

采用密度泛函理论PBE0方法在6-31G(d, p) 基组水平上对比研究并六苯纳米环[6]CA及BN取代纳米环[6]CA-BN的几何结构及电子性质. 同时探讨锂离子掺杂对不同体系的芳香性、前线分子轨道、电子吸收光谱及传输性质的影响. 通过电离势、亲合势及重组能的计算, 预测纳米环体系得失电子的能力及传输性能. 结果表明:[6]CA的能隙很小, BN取代后, 能隙明显增大; 锂离子掺杂到两种纳米环中, 在不明显改变前线分子轨道分布的前提下, 几乎同步降低了最高占据轨道、 最低未占据轨道能级, 锂离子掺杂使载流子传输性能得到很大改善; 电子吸收光谱拟合发现, BN取代使吸收光谱很大程度蓝移, 吸收强度明显减小; 而锂离子掺杂对光谱的强度及吸收范围没有明显影响. 关键词： 碳纳米环 硼氮纳米环 锂离子掺杂 密度泛函理论     

Tuning the electronic properties of the fullerene C<Subscript>20</Subscript> cage via silicon impurities

The fullerene C₂₀ represents one of the most active classes of nanostructures, and they have been widely used as active materials for important applications. In this study, we investigate and discuss the tuning of the electronic properties of the fullerene C₂₀ cage via various consternations and locations of silicon atoms. All calculations are based on the density functional theory (DFT) at the B3LYP/3-21G level through the Gaussian 09W program package. The optimized structures, density of state (DOS) analysis, total energies, dipole moments, HOMO energies, Fermi level energies, LUMO energies, energy gaps, and the work functions were performed and discussed. Our results show that the electronic properties of C₂₀ cage do not only depend on the silicon impurity concentrations, but also depend on the geometrical pattern of silicon impurities in the C₂₀ cage. The tuning of the electronic properties leads to significant changes in the charge transport and the absorption spectra for C₂₀ cage via engineering the energy gap. So, we suggest that substitutional impurities are the best viable option for enhancement of desired electronic properties of C₂₀ cage for using these structures in nanoelectronics and solar cell applications.     

Are transition-metal borides promising for Na ion batteries? A first-principles study on transition-metal boride monolayer

Although two-dimensional (2D) materials have been proposed as the promising candidates for Na ion batteries (NIBs), electrode materials with high specific capacity and moderate diffusion energy barriers are still scare. Here, we firstly demonstrated that transition-metal borides (TMB) are much more promising electrode materials than other transition metal compounds. Density functional theory (DFT) calculations are performed to investigate the electronic properties and Na storage capability of TMB monolayer, which is realized in recent experiments. TMB monolayer forms strong chemical interaction with Na atoms, and the diffusion energy barrier of Na atoms is much lower than LIBs. Importantly, TMB monolayer exhibits a very high Na storage capacity. Such exceptional properties, including high stoichiometry (namely TMBNa₂), excellent electronic conductivity, moderate Na diffusion and high operating voltage, endow TMB monolayers as very promising anode materials for NIBs.     

Hexagonal boron phosphide and boron arsenide van der Waals heterostructure as high-efficiency solar cell

The rapid development of two-dimensional (2D) materials offers new opportunities for 2D ultra-thin excitonic solar cells (XSCs). The construction of van der Waals heterostructure (vdWH) is a recognised and effective method of integrating the properties of single-layer 2D materials, creating particularly superior performance. Here, the prospects of h-BP/h-BAs vdW heterostructures in 2D excitonic solar cells are assessed. We systematically investigate the electronic properties and optical properties of heterogeneous structures by using the density functional theory (DFT) and first-principles calculations. The results indicate that the heterogeneous structure has good optoelectronic properties, such as a suitable direct bandgap and excellent optical absorption properties. The calculation of the phonon spectrum also confirms the well-defined kinetic stability of the heterstructure. We design the heterogeneous structure as a model for solar cells, and calculate its solar cell power conversion efficiency which reaches up to 16.51% and is higher than the highest efficiency reported in organic solar cells (11.7%). Our work illustrates the potential of h-BP/h-BAs heterostructure as a candidate for high-efficiency 2D excitonic solar cells.     

Electronic and transport properties of V-shaped defect zigzag MoS_2 nanoribbons

Based on the nonequilibrium Green＇s function （NEGF） in combination with density functional theory （DFT） calcu- lations, we study the electronic structures and transport properties of zigzag MoS2 nanoribbons （ZMNRs） with V-shaped vacancy defects on the edge. The vacancy formation energy results show that the zigzag vacancy is easier to create on the edge of ZMNR than the armchair vacancy. Both of the defects can make the electronic band structures of ZMNRs change from metal to semiconductor. The calculations of electronic transport properties depict that the currents drop off clearly and rectification ratios increase in the defected systems. These effects would open up possibilities for their applications in novel nanoelectronic devices.     

能带反折叠方法研究进展

基于密度泛函理论的第一性原理方法已经成为人们研究材料结构、性质以及进行新功能材 料设计的重要手段。对于掺杂和界面体系，人们常常需要使用超胞来描述。超胞的使用导致能带 折叠，从而掩盖能带结构的重要特征，为人们分析掺杂和界面效应对材料能带结构的影响带来困 难。本文概述了超胞导致的能带折叠现象，重点介绍了基于平面波和原子轨道的能带反折叠方法、 声子能带反折叠方法及相关计算工具，给出了该方法在掺杂和界面体系电子、声子能带结构方面 应用的例子，并对该方法进行了展望。     

Migration of adatom adsorption on graphene using DFT calculation

DFT calculations of various atomic species on graphene sheet are investigated as prototypes for the formation of nano-structures on graphene. We investigate computationally the adsorption energies and migration energies in adsorption sites on graphene sheet for many atomic species, including transition metals, noble metals, nitrogen and oxygen, from atomic number 1 to 83, using the DFT calculation. The calculations are done for adatoms at three sites having symmetry, H6, B and T on a 3×3 super cell. For adsorption energy and migration energy, we performed a study that covered almost all the periodic table. The calculated results show that adsorption for metal and transition metal elements is mainly on the H6-site, whereas nonmetallic elements showed a tendency to adsorb on the B-site. When we consider a metal-graphene junction, not only the adsorption energy but also the migration energy is important. We estimate the minimum limit of the migration energy of the adatom. We found that 3d transition metals and some nonmetallic elements had very high migration energy. Our calculation will be very helpful for experimental groups that are considering the choice of electrode materials for metal-graphene junctions, and in designing nano devices, nano wires and nano switches.     

Investigation of excitonic states effects on optoelectronic properties of Sb2Se3 crystal for broadband photo-detector by highly accurate first-principles approach

The rapid demand of photodetector is increasing day by day due to its versatility of applications that affect our lives. However, it is still very challenging to produce low-cost high-performance broadband photo-detector that can detect light from near infrared to the ultraviolet frequency range for medical diagnosis and visible light communication applications. Regarding this, low-cost antimony selenide (Sb₂Se₃), with direct energy gap and strong light absorption over a wider range from near infrared to ultraviolet frequency, is considered a promising candidate material for such kind of applications. Therefore, to expose its hidden potential, detailed analysis of its structural, electronic and optical properties is very essential. To accomplish this purpose, different schemes of the first-principles calculations are used in this study. Structural properties of Sb₂Se₃ are calculated by first-principles methods realized within density functional theory (DFT) framework. Whereas, to compute the quasiparticle (QP) band structure, excitonic and optical properties, many-body perturbation theory (MBPT) based on one-shot GW (G₀W₀) and Bethe-Salpeter equation (G₀W₀-BSE) approaches are used. Our DFT calculations show that Wu-Cohen GGA (WC-GGA) reproduces lattice parameters of Sb₂Se₃ material consistent with the experimental measurements. Similarly, G₀W₀ calculations confirm the Sb₂Se₃ a direct bandgap energy material of 1.32 eV and show good agreement with the experimental results. Similarly, the results on the optical properties of Sb₂Se₃ with the inclusion of electron-hole interaction show that the exciton energy of the material is 1.28eV while its corresponding plasma energy is 10.86 eV. These values show that the investigated material can absorb photons from near infrared to ultraviolet wavelengths. It is, therefore, anticipated that this material will be useful for new-generation optoelectronic applications from near infrared to ultraviolet wavelengths.     

Exploring at nanoscale from first principles

Systems at the nanoscale can exhibit distinctive and unexpected properties in electrical, magnetic, mechanical, and chemical aspects. Understanding these properties not only is of importance from the fundamental scientific view but also offers great opportunities for future applications. Theoretical calculations can provide important information to interpret, modify, and predict the novel properties of objects at the nanoscale and therefore play a significant role in the process of exploring the nano world. In this review, six different areas are briefly presented, namely, prediction of new stable structures, modification of properties (especially the electronic structures), design of novel devices for applications, the structures and catalytic effects of clusters, the mechanical and transport properties of gold nanowires, and improvement of materials for hydrogen storage. Based on these examples, we show what can be done and what can be found in the investigations of nanoscale systems with participation of theoretical calculations.      

Mechanical properties,lattice thermal conductivity,infrared and Raman spectrum of the fullerite C24

Lightweight carbon materials with excellent thermal and mechanical properties have important applications in aerospace industry. In this study, the stability, mechanical properties, lattice thermal conductivity, electronic structure, infrared and Raman spectrum of sp³ hybridized low-density fullerite C₂₄ were investigated according to density functional theory (DFT) calculations. It was found that the fullerite C₂₄ was both thermodynamic and dynamic stable. Quasi-harmonic approximation and Grüneisen parameter calculations clarified why the fullerite C₂₄ had a positive thermal expansion coefficient at low temperature. The fullerite C₂₄ also exhibited excellent mechanical properties. Interestingly, the Vickers hardness of carbon allotropes was found to almost be linear proportional to the density of a carbon material. HSE06 electronic structure calculations showed that it was a semiconductor with direct bandgap of 2.56 eV. Anharmonic lattice dynamic calculations showed that its thermal conductivity was higher than semiconductor silicon. Besides, Raman and infrared active modes as well as the corresponding spectra were presented.     

Synthesis,Properties, and Applications of 2-D Materials: A Comprehensive Review

Recent advances in atomically thin two-dimensional (2-D) materials have led to a variety of promising future technologies for post-CMOS nanoelectronics and energy generation. This review is an attempt to thoroughly illustrate the current status and future prospects for 2-D materials other than graphene (e.g., BN nanosheets, MoS₂, NbSe₂, WS₂, etc.), which have already been contemplated for both low-end and high-end technological applications. An overview of the different synthesis techniques for 2-D materials is presented here, with an exploration of the potential for developing methods of controllable large scale synthesis. Furthermore, we summarize the underlying theories which correlate the structural and physical properties of 2-D materials with their state-of-the-art applications. Finally, we show that utilizing the unprecedented properties arising from these materials would lead to innovative devices. Such devices would significantly reduce both device dimensions and power consumption, as necessary for the creation of tomorrow's sustainable technology.     

An overview of engineered porous material for energy applications: a mini-review

The ordered porous materials, developed using various templating materials, have generated huge interest among the electrochemist community due to their plenty of unique properties and functionalities that can be effectively applied in optoelectronic devices. Mesoporous materials possess excellent opportunities in energy storage and energy conversion applications due to their extraordinarily high surface area and large pore size. These properties may enhance the performance of porous materials in terms of lifetime and stability, energy and power density. In this review, we have tried to club the fields of optoelectronics and mesoporous materials. Also, we have summarised the primary methods for preparing mesoporous materials using various templates and described their applications as electrodes and catalysts in fuel cells, solar fuel production, dye-sensitised solar cells, perovskite, supercapacitors and rechargeable batteries. Finally, we have highlighted the research and development challenges of mesoporous materials those need to be overcome to enhance their contribution in renewable energy applications.     

Preparation and characterization by infrared emission spectroscopy and applications of new mineral-based composite materials of biomedical interest

New composite materials based on clay minerals had been prepared by reductive calcination. These materials exhibit very strong infrared (IR) emission at quite low temperatures. The structural properties and emission capabilities of the new materials have been studied by various theoretical and experimental methods. In addition, a brief overview of the medical and other practical applications of IR-emitting materials is presented. The basic principles of IR emission spectroscopy are discussed with special respect to low temperatures (close to human-body temperature). Furthermore, DFT calculations on a kaolinite structure of chemical composition of [Al₄Si₄ O₈(OH)₁₆]^4? have been performed. The calculated bond distances and IR spectrum are in good agreement with experimental observations. Structural and compositional characterization of the new composite materials have been performed by various structural analytical methods. An interesting effect on the IR phosphorescence of composite samples has been established. After 2 hours of IR light exposure at room temperature from the FT-IR spectrometer, the composite materials exhibited enhanced emission of IR radiation with relaxation time about 40 min. Finally, two practical applications of the composites have been investigated, namely polyamide-based fabrics and rubber preservatives.     

Computational quantum magnetism: Role of noncollinear magnetism

We are witnessing today a golden age of innovation with novel magnetic materials and with discoveries important for both basic science and device applications. Computation and simulation have played a key role in the dramatic advances of the past and those we are witnessing today. A goal-driving computational science—simulations of every-increasing complexity of more and more realistic models has been brought into greater focus with greater computing power to run sophisticated and powerful software codes like our highly precise full-potential linearized augmented plane wave (FLAPW) method. Indeed, significant progress has been achieved from advanced first-principles FLAPW calculations for the predictions of surface/interface magnetism. One recently resolved challenging issue is the role of noncollinear magnetism (NCM) that arises not only through the SOC, but also from the breaking of symmetry at surfaces and interfaces. For this, we will further review some specific advances we are witnessing today, including complex magnetic phenomena from noncollinear magnetism with no shape approximation for the magnetization (perpendicular MCA in transition-metal overlayers and superlattices; unidirectional anisotropy and exchange bias in FM and AFM bilayers; constricted domain walls important in quantum spin interfaces; and curling magnetic nano-scale dots as new candidates for non-volatile memory applications) and most recently providing new predictions and understanding of magnetism in novel materials such as magnetic semiconductors and multi-ferroic systems.     

Experimental Synthesis of Strained Monolayer Silver Arsenide on Ag(111)Substrates

Two-dimensional(2 D) materials are playing more and more important roles in both basic sciences and industrial applications. For 2 D materials, strain could tune the properties and enlarge applications. Since the growth of 2 D materials on substrates is often accompanied by strain, the interaction between 2 D materials and substrates is worthy of careful attention. Here we demonstrate the fabrication of strained monolayer silver arsenide(AgAs) on Ag(111) by molecular beam epitaxy, which shows one-dimensional stripe structures arising from uniaxial strain.The atomic geometric structure and electronic band structure are investigated by low energy electron diffraction,scanning tunneling microscopy, x-ray photoelectron spectroscopy, angle-resolved photoemission spectroscopy and first-principle calculations. Monolayer AgAs synthesized on Ag(111) provides a platform to study the physical properties of strained 2 D materials.     

Density functional theory study on the adsorption of alkali metal ions with pristine and defected graphene sheet

The graphene-based materials along with the adsorption of alkali metal ions are suitable for energy conversion and storage applications. Hence in the present work, we have investigated the structural and electronic properties of pristine and defected graphene sheet upon the adsorption of alkali metal ions (Li⁺, Na⁺, and K⁺) using density functional theory (DFT) calculations. The presence of vacancies or vacancy defects enhances the adsorption of alkali ions than the pristine sheet. From the obtained results, it is found that the adsorption energy of Li⁺ on the vacancies defected graphene sheet is higher (3.05?eV) than the pristine (2.41?eV) and Stone–Wales (2.50?eV) defected sheets. Moreover, the pore radius of the pristine and defected graphene sheets are less affected by metal ions adsorption. The increase in energy gap upon the adsorption of metal ions is found to be high in the vacancy defected graphene than that of other sheets. The metal ions adsorption in the defective vacancy sheets has high charge transfer from metal ions to the graphene sheet. The bonding characteristic between the metal ions and graphene sheet are analysed using QTAIM analysis. The influence of alkali ions on the electronic properties of the graphene sheet is examined from the Total Density of States (TDOS) and Partial Density of States (PDOS).