Self-consistent-charge Density-functional Tight-binding Research Articles

Benchmark Investigation of SCC-DFTB against Standard and Hybrid DFT to Model Electronic Properties in Two-Dimensional MOFs for Thermoelectric Applications.

Recent studies have shown that metal-organic frameworks (MOFs) have potential as thermoelectric materials, and the topic has received increasing attention. The main motivation for this project is to further our knowledge of thermoelectric properties in MOFs and find which available self-consistent-charge density functional tight binding (SCC-DFTB) method can best predict (at least trends in) the electronic properties of MOFs at a lower computational cost than standard density functional theory (DFT). In this work, the electronic properties of monolayer, serrated, AA-stacked, and/or AB-stacked Zn3C6O6, Cd3C6O6, Zn-NH-MOF─for which no previous calculations of thermoelectric performance exist─and Ni3(HITP)2 MOFs are modeled with DFT-PBE, DFT-HSE06, GFN1-xTB, GFN2-xTB, and DFTB-3ob/mio. The band structures, density of states, and their relative orbital contributions, as well as the electrical conductivity, Seebeck coefficient, and power factor, are compared across methods and geometries. Our results suggest that GFN-xTB is adequate to predict the MOFs' band structure shape and density of states but not band gap. Our calculations further indicate that Zn3C6O6, Cd3C6O6, and Zn-NH-MOF have higher power factor values than Ni3(HITP)2, one of the highest performing synthesized MOFs, and are therefore promising for thermoelectric applications.

A multi-scale computational investigation of cationic dye interaction with rutile TiO2: An interconnected simulation approach

Metal oxides have increasingly been employed for water pollution remediation. In the present investigation, the adsorptive characteristics of three cationic dyes, rhodamine B (RB), safranin O (SO), and methylene blue (MB), on the (110) surface of rutile titanium dioxide in an aqueous milieu were scrutinized. Utilizing Density Functional Theory (DFT), the reactivity of these organic compounds was evaluated by computing parameters such as molecular frontier orbital energies, energy gap (ΔEgap), electronegativity (χ), chemical hardness (η), chemical softness (σ), electrophilicity (ω), nucleophilicity, electron transfer fraction (ΔN), and Fukui indices. Findings demonstrated that RB exhibited superior reactivity and adsorptive capacity in comparison to MB and SO. Self-Consistent Charge Density-Functional Tight-Binding (SCC-DFTB) simulations revealed that RB engaged in the most potent interactions with the TiO2(110) surface, with interaction energies following the sequence RB (−1.12 eV) > MB (−1.07 eV) > SO (−1.01 eV). Furthermore, the most energetically favorable adsorption configurations for these dyes were elucidated through Molecular Dynamics (MD) simulations. Adsorption energies calculated via MD simulations corroborated that the TiO2 (110) surface possessed high adsorptive capabilities for these cationic dyes, particularly a stronger affinity for RB. The study provides comprehensive insights into the molecular-level interactions between cationic dyes and rutile TiO2, thereby contributing valuable information for the optimization of metal oxide-based water pollution treatment technologies.

Structure and electrical properties of bilayer zigzag silicene nanoribbons depending on stone-wales and applied electric fields by SCC-DFTB method

The influence of geometry and electrical properties of Stone-Wales (SW) defects and an applied electric field on bilayer zigzag silicene nanoribbons (ZSiNRs) were investigated using the self-consistent charge density functional tight-binding (SCC-DFTB) method. The results show that concave deformation occurs at SW defects, leading to varying degrees of disruption in the original symmetrical structure. The overall stability of the marginal Stone-Wales (MSW) nanoribbons surpasses that of the central Stone-Wales (CSW) nanoribbons, SW-II type defects are prone to form in bilayer nanoribbons. The band gap of MSW defective nanoribbons expands significantly, realizing the transition from metallic to semi-metallic and semi-conductor properties. The electrons are transferred from the inner to the outer side of the nanoribbons, with a higher prevalence of defect nanoribbons compared to those that are perfect. The electric field intensity significantly alters the properties of both MSW-I and MSW-II defective nanoribbons.

Structure and electrical properties of double-walled silicon nanotubes depending on 585 defects and applied electric fields by SCC-DFTB method

The geometric structural and electronic properties of 585 defective double-walled silicon nanotubes (DWSiNTs) by using the self-consistent charge density functional tight-binding (SCC-DFTB) method. Furthermore, we investigated the impact of external electric field and intensity on the electronic properties. After the relaxation of perfect tubes, the structure of the tube changes significantly, and the winding direction of the tube wall changes. The buckling value of the tube wall is most closely related to the geometric shape and atomic arrangement order of tubes. The overall stability of zigzag tubes is higher than armchair tubes, and (6,6)@(10,10) stability is significantly affected by defects. The partially defected zigzag tubes change from direct band gap semiconductor properties to indirect band gap semi-metal properties. A transformation of the semiconductor-semimetal properties, direct-indirect band gap of DWSiNTs is realized. The charge transfer amplitude of the defect tubes is greater than the perfect tube. The applied electric field makes the stability of all tubes decrease linearly, and the stability of the defect tubes is higher than the perfect tube. Part of the electric field strength changes the defect tubes from semiconductor properties to semi-metal properties, and semi-metal properties to metal properties. These theoretical studies provide a reference for the preparation and future application of DWSiNTs.

Influence of Stone-Wales defects on the structural and electronic properties of single-walled silicon nanotubes by SCC-DFTB calculations

In this work, using the self-consistent charge density functional tight-binding (SCC-DFTB) approach, we explored the effects of Stone-Wales (SW) defects on the structure and electronic properties of perfect single-walled silicon nanotubes(SWSiNTs), including zigzag (n1,0) (8≤n1≤16), armchair (n2,n2) (5≤n2≤10), and chiral (2n3,n3) (3≤n3≤8). We found that the presence of SW defects leads to changes in bond length and bond angle, resulting in structural changes at the defect site. However, nanotubes still exhibit tubular and hexagonal structures. Also, the defect structure of zigzag and armchair SW-II defective tubes is symmetrical, which means that the bond length of the Si-Si bond is equivalent to that of its symmetric bond. Besides, after introducing the SW-II defect, zigzag and chiral tubes become more stable, but the stability of armchair tubes with small diameter is reduced. The introduction of SW-Ⅰ and SW-Ⅱ defects transforms armchair SiNTs from semiconductor into semi-metallic properties. Moreover, for a perfect structure, the charge moves from inside out along the radial direction of the tube and the amount of charge is distributed in an axisymmetric manner. After introducing SW defects, the range of charge transfer is expanded, SW-Ⅱ defective structures appear inward deviation, and the atoms near the defect change from regular arrangement to inward aggregation. This work may provide a new way to adjust the electronic properties of SWSiNTs and open up wider applications in nanoelectronic devices.

Computational Exploration of Phenolic Compounds in Corrosion Inhibition: A Case Study of Hydroxytyrosol and Tyrosol.

The corrosion of materials remains a critical challenge with significant economic and infrastructural impacts. A comprehensive understanding of adsorption characteristics of phytochemicals can facilitate the effective design of high-performing environmentally friendly inhibitors. This study conducted a computational exploration of hydroxytyrosol (HTR) and tyrosol (TRS) (potent phenolic compounds found in olive leaf extracts), focusing on their adsorption and reactivity on iron surfaces. Utilizing self-consistent-charge density-functional tight-binding (SCC-DFTB) simulations, molecular dynamics (MD) simulations, and quantum chemical calculations (QCCs), we investigated the molecules' structural and electronic attributes and interactions with iron surfaces. The SCC-DFTB results highlighted that HTR and TRS coordinated with iron atoms when adsorbed individually, but only HTR maintained bonding when adsorbed alongside TRS. At their individual adsorption, HTR and TRS had interaction energies of -1.874 and -1.598 eV, which became more negative when put together (-1.976 eV). The MD simulations revealed parallel adsorption under aqueous and vacuum conditions, with HTR demonstrating higher adsorption energy. The analysis of quantum chemical parameters, including global and local reactivity descriptors, offered crucial insights into molecular reactivity, stability, and interaction-prone atomic sites. QCCs revealed that the fraction of transferred electron ∆N aligned with SCC-DFTB results, while other parameters of purely isolated molecules failed to predict the same. These findings pave the way for potential advancements in anticorrosion strategies leveraging phenolic compounds.

Unraveling the anti-corrosion mechanisms of a novel hydrazone derivative on steel in contaminated concrete pore solutions: An integrated study

IntroductionCorrosion-induced deterioration of infrastructure is a growing global concern. The development and application of corrosion inhibitors are one of the most effective approaches to protect steel rebar from corrosion. Hence, this study focuses on a novel hydrazone derivative, (E)-N′-(4-(dimethylamino)benzylidene)-2-(5-methoxy-2-methyl-1H-indol-3-yl)aceto-hydrazide (HIND), and its potential application to mitigate corrosion in steel rebar exposed to chloride-contaminated concrete pore solutions (ClSCPS). ObjectivesThe research aims to evaluate the anti-corrosion capabilities of HIND on steel rebar within a simulated corrosive environment, focusing on the mechanisms of its inhibitory effect. MethodsThe corrosion of steel rebar exposed to the ClSCPS was studied through weight loss and electrochemical methods. The surface morphology of steel rebar surface was characterized by FE-SEM-EDS, AFM; oxidation states of the steel rebar and crystal structures were examined using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) methods. Further, experimental findings were complemented by theoretical studies using self-consistent-charge density-functional tight-binding (SCC-DFTB) simulations. The performance of HIND was monitored at an optimal concentration over a period of 30 days. ResultsThe results indicated a significant reduction in steel rebar corrosion upon introducing HIND. The inhibitor molecules adhered to the steel surface, preventing further deterioration and achieving an inhibition efficiency of 88.4% at 0.5 mmol/L concentration. The surface morphology analysis confirmed the positive effect of HIND on the rebar surface, showing a decrease in the surface roughness of the steel rebar from 183.5 in uninhibited to 50 nm in inhibited solutions. Furthermore, SCC-DFTB simulations revealed the presence of coordination between iron atoms and HIND active sites. ConclusionThe findings demonstrate the potential of HIND as an effective anti-corrosion agent in chloride-contaminated environments. Its primary adsorption mechanism involves charge transfer from the inhibitor molecules to iron atoms. Therefore, applying HIND could be an effective strategy to address corrosion-related challenges in reinforced infrastructure.

Effects of Stone-Wales defects on structure and electrical properties of double-walled silicon nanotubes by SCC-DFTB method

In this work, the geometric structure, system stability, electrical properties and charge distribution of zigzag double-walled silicon nanotubes (DWSiNTs) (nin,0)@(nout,0) (nin = 5–7, nout = 8–13) perfect tubes and defective tubes with three types of Stone-Wales (SW) defects were studied using the self-consistent charge density functional tight-binding (SCC-DFTB) method. The change of the chirality index between the inner and outer walls was simulated. The results show that the symmetry of the structure disappears, and the warping of the tube wall changes from order to disorder after introducing SW defects. The warps of outer tube are obviously higher than that of inner tube. The perfect tubes with inner wall chirality index (6,0) are more stable than other tubes. SW defects of outer wall tubes have a higher effect on system stability than those of inner wall tubes. The difference of inner and outer wall chirality indices plays an obvious role in regulating the energy gap of the system, half of which are near-metal properties and the other half semiconductor properties, and the regulation range is 0.1075–0.8519 eV. All types of SW defects at all locations have a certain regulatory effect on the energy gap of DWSiNTs, and the effect of type III defect is the most obvious. The effect of atomic charge redistribution in the tube is related to the structure, and the charge transfer in a perfect tube is symmetrical. The number of electrons obtained at the defect is increased, and the electronegativity is stronger, due to the curvature of local atoms produced at the defect. This study provides a reference for the preparation and future application of DWSiNTs.

Shadow Molecular Dynamics and Atomic Cluster Expansions for Flexible Charge Models.

A shadow molecular dynamics scheme for flexible charge models is presented where the shadow Born-Oppenheimer potential is derived from a coarse-grained approximation of range-separated density functional theory. The interatomic potential, including the atomic electronegativities and the charge-independent short-range part of the potential and force terms, is modeled by the linear atomic cluster expansion (ACE), which provides a computationally efficient alternative to many machine learning methods. The shadow molecular dynamics scheme is based on extended Lagrangian (XL) Born-Oppenheimer molecular dynamics (BOMD) [Eur. Phys. J. B 2021, 94, 164]. XL-BOMD provides stable dynamics while avoiding the costly computational overhead associated with solving an all-to-all system of equations, which normally is required to determine the relaxed electronic ground state prior to each force evaluation. To demonstrate the proposed shadow molecular dynamics scheme for flexible charge models using atomic cluster expansion, we emulate the dynamics generated from self-consistent charge density functional tight-binding (SCC-DFTB) theory using a second-order charge equilibration (QEq) model. The charge-independent potentials and electronegativities of the QEq model are trained for a supercell of uranium oxide (UO2) and a molecular system of liquid water. The combined ACE+XL-QEq molecular dynamics simulations are stable over a wide range of temperatures both for the oxide and for the molecular systems and provide a precise sampling of the Born-Oppenheimer potential energy surfaces. Accurate ground Coulomb energies are produced by the ACE-based electronegativity model during an NVE simulation of UO2, predicted to be within 1 meV of those from SCC-DFTB on average during comparable simulations.

Unraveling Bonding Mechanisms and Electronic Structure of Pyridine Oximes on Fe(110) Surface: Deeper Insights from DFT, Molecular Dynamics and SCC-DFT Tight Binding Simulations.

The development of corrosion inhibitors with outstanding performance is a never-ending and complex process engaged in by researchers, engineers and practitioners. The computational assessment of organic corrosion inhibitors' performance is a crucial step towards the design of new task-specific materials. Herein, the electronic features, adsorption characteristics and bonding mechanisms of two pyridine oximes, namely 2-pyridylaldoxime (2POH) and 3-pyridylaldoxime (3POH), with the iron surface were investigated using molecular dynamics (MD), and self-consistent-charge density-functional tight-binding (SCC-DFTB) simulations. SCC-DFTB simulations revealed that the 3POH molecule can form covalent bonds with iron atoms in its neutral and protonated states, while the 2POH molecule can only bond with iron through its protonated form, resulting in interaction energies of -2.534, -2.007, -1.897, and -0.007 eV for 3POH, 3POH+, 2POH+, and 2POH, respectively. Projected density of states (PDOSs) analysis of pyridines-Fe(110) interactions indicated that pyridine molecules were chemically adsorbed on the iron surface. Quantum chemical calculations (QCCs) revealed that the energy gap and Hard and Soft Acids and Bases (HSAB) principles were efficient in predicting the bonding trend of the molecules investigated with an iron surface. 3POH had the lowest energy gap of 1.706 eV, followed by 3POH+ (2.806 eV), 2POH+ (3.121 eV), and 2POH (3.431 eV). In the presence of a simulated solution, MD simulation showed that the neutral and protonated forms of molecules exhibited a parallel adsorption mode on an iron surface. The excellent adsorption properties and corrosion inhibition performance of 3POH may be attributed to its low stability compared to 2POH molecules.

C60 adsorption on defective Si (1 0 0) surface having one missed dimer from atomic simulations at electrical level

The adsorption geometry and electronic information of C60 onto reconstructed Si (100) surface having two types of missed dimers were investigated from self-consistent charge density functional tight-binding (SCC-DFTB) simulations. The C60 molecular orientation being relative to the defective Si surface, bonding form, and the number and distribution of dimers in the silicon surface, greatly affect the packing configurations in the C60/Si (100) systems. Charge-difference density and Mulliken populations analysis indicated that C60 was chemically bound to the silicon substrate by C-Si covalent bonds and the bond energy of short CSi covalent bonds is higher than others. The different adsorption configurations of C60/Si systems have different chemical potentials, implying their various applications in the redox reactivity.

Island-Type Graphene-Nanotube Hybrid Structures for Flexible and Stretchable Electronics: In Silico Study.

Using the self-consistent charge density functional tight-binding (SCC-DFTB) method, we study the behavior of graphene-carbon nanotube hybrid films with island topology under axial deformation. Hybrid films are formed by AB-stacked bilayer graphene and horizontally aligned chiral single-walled carbon nanotubes (SWCNTs) with chirality indices (12,6) and 1.2 nm in diameter. In hybrid films, bilayer graphene is located above the nanotube, forming the so-called "islands" of increased carbon density, which correspond to known experimental data on the synthesis of graphene-nanotube composites. Two types of axial deformation are considered: stretching and compression. It has been established that bilayer graphene-SWCNT (12,6) hybrid films are characterized by elastic deformation both in the case of axial stretching and axial compression. At the same time, the resistance of the atomic network of bilayer graphene-SWCNT (12,6) hybrid films to failure is higher in the case of axial compression. Within the framework of the Landauer-Buttiker formalism, the current-voltage characteristics of bilayer graphene-SWCNT (12,6) hybrid films are calculated. It is shown that the slope of the current-voltage characteristic and the maximum values of the current are sensitive to the topological features of the bilayer graphene in the composition of graphene-SWCNT (12,6) hybrid film. Based on the obtained results, the prospects for the use of island-type graphene-nanotube films in flexible and stretchable electronic devices are predicted.

Computational insights into the adsorption mechanisms of anionic dyes on the rutile TiO2 (1 1 0) surface: Combining SCC-DFT tight binding with quantum chemical and molecular dynamics simulations

Metal oxides are gaining momentum rapidly for application in water pollutant remediation. In this study, the adsorption proprieties of two anionic dyes, i.e., acid yellow 36 (AY36) and acid orange 6 (AO6) on the (110) surface of rutile titanium dioxide (TiO2) in an aqueous medium were investigated using computational methods. The density functional theory (DFT) was used to determine the reactivity of organic molecules by calculating the frontier molecular orbital energies, energy gap (ΔEgap), chemical hardness (η), chemical softness (σ), electronegativity (χ), chemical potential (μ), electrophilicity (ω), the fraction of electrons transferred (ΔN), back-donation energy (ΔEback-donation), Mulliken charge, and Fukui indices. The obtained results showed that the AY36 molecule is more reactive than the AO6 molecule and may have a good adsorption capability compared to the AO6 dye. The most favorable adsorption configurations of AY36 and AO6 molecules were investigated using molecular dynamics (MD) simulation. The calculated interaction energies by MD simulation showed that the TiO2 (110) surface has a high sensitivity to interact with the two anionic dyes, with more affinity toward the AY36 molecule. Furthermore, to get deep insights into the chemistry of interactions between the anionic dyes and the TiO2 (110) surface, the self-consistent charge density functional tight-binding (SCC-DFTB) method was carried out. Results showed that anionic dyes adsorbed on the TiO2 (110) surface by forming covalent bonds between oxygen atoms of the sulfonic group and Ti atoms. Theoretical insights from this work would serve as a guide for researchers to explore the application of oxides in water pollutant remediation.

Assessment of the inhibitive performance of a hydrazone derivative for steel rebar in a simulated concrete medium: Establishing the inhibition mechanism at an experimental and theoretical level

In the present work, a low-cost and practical approach based on an eco-friendly corrosion inhibitor is suggested for protecting steel rebar. To this end, a new hydrazone derivative, namely N'-(furan-2-ylmethylene)-2-(5-methoxy-2-methyl-1H-indol-3-yl) acetohydrazide (FMAH) was synthesized and its corrosion inhibition characteristics for steel rebar (STR) in chloride contaminated simulated concrete pore solutions (ClSCPS) were evaluated using experimental and theoretical methods. The electrochemical studies, which were conducted at several periods ranging from 1 h to 30 d indicated that the addition of FMAH to the ClSCPS significantly improved the passive film formation. It considerably increased film and charge transfer resistances at an early immersion stage, then decreased at longer immersion periods. Potentiodynamic polarization curves (PPCs) revealed that the investigated compound could be categorized as a mixed inhibitor with a predominance anodic effect. The gravimetric and potentiodynamic polarization studies confirmed corrosion inhibition efficiencies of 80.9% and 81.1%, respectively, for 1.0 mmol.L-1 FMAH after 30 d of exposure. Surface characterization of corroded and inhibited STR surface by X-ray photoelectron spectroscopy (XPS), SEM coupled with EDS, Raman spectroscopy, atomic force microscopy (AFM) and X-ray diffraction spectroscopy (XRD) revealed that inhibitor molecules chemically adsorbed on the STR forming a highly resistant protective layer against corrosive species. Theoretical modeling of inhibitor’s adsorption on the iron surface by the self-consistent-charge Density-functional tight-binding (SCC-DFTB) indicated the formation of several covalent bonds between carbon and oxygen atoms with the iron atoms. The analysis of FMAH-Fe (110) adsorption systems by projected density of states revealed that FMAH molecules adsorbed on the iron surface through a charge transfer process. The interesting results from the present work would open great opportunities for exploring the anti-corrosion performance of the investigated compound in concrete.

Self-consistent charge density functional tight-binding (SCC-DFTB) parameterization and validation for Ti50Pd50-XRuX alloys

Titanium-palladium based systems are in high demand currently, particularly for the development of high-temperature shape memory alloys with a unique application in the aerospace industry. In particular, the Ti50Pd50-XRuX is found to be one of the promising alloys. This is due to their shape memory effect and superelasticity. Previous studies revealed that these alloys are mechanically stable above 25 at. % Ru with a positive C′ at 0 K. So, an understanding of its transformation temperature behavior is required, which is currently not clear. The self-consistent-charge density functional tight-binding (SCC-DFTB) approach was used to develop parameters for Ti50Pd50-XRuX employing the parameterization technique. The structural, electronic and elastic properties were determined to check their relative stability on derived potentials using DFTB + code. As part of the validation for the developed set, the results were reproducible to within 5 % agreement as compared with other theoretical findings. Furthermore, the SCC sets of parameters were also used to determine the lattice expansions and check the transformation temperature of ternary Ti50Pd50-XRuX. It was observed that the addition of Ru reduces the transformation temperature. The findings imply that the SCC-DFTB approach was able to predict the stability and transformation behavior of Ti50Pd50-XRuX alloys.

Predicting Material Properties of Methane Hydrates with Cubic Crystal Structure Using Molecular Simulations

AbstractFormation of gas hydrates is an important feature of water systems. It occurs undesirably in natural gas pipelines, but also in deep‐sea deposits and unfreezing permafrost. However, the natural occurrence is of particular interest because methane hydrates have one of the highest energy densities of all naturally occurring forms of methane. Therefore, an accurate description of its thermodynamic properties is required. In this work, we demonstrate how the material properties of methane hydrate can be more easily calculated compared to ab initio methods. Furthermore, it is shown how the material properties depend on the cage occupancy by using the comparably fast self‐consistent‐charge density‐functional tight‐binding (SCC‐DFTB) method. The cell potential is calculated and compared to a numerical as well as an ab initio model, and is in good agreement with the literature.

Effects of edge hydrogenation and applied electric field on the structure and electrical properties of zigzag silicene nanoribbons by SCC-DFTB calculations

The effects of edge hydrogenation and applied electric field in different directions on the geometrical structure and electrical properties of zigzag silicene nanoribbons (ZSiNRs) with different period widths (width = 2,3,4) were investigated by using a self-consistent charge density functional tight-binding (SCC-DFTB) method. The results show that the degree of warpage of the ZSiNRs is significantly changed by hydrogenation, while the bond length and bond angle are less affected. The edge hydrogenation reduces the Si-dangling bonds in the nanoribbons, which increased the binding energy of nanoribbon and enhanced system stability. In the absence of an electric field, the unhydrogenated nanoribbons with different period widths all exhibit semiconducting properties, and the hydrogenated nanoribbons exhibit metallic or semi-metallic properties. Under the vertical external electric field in the z-direction, the stability and energy gap of the unhydrogenated nanoribbons are sensitive to the change of strength, and the oscillation fluctuation is large. With the increase of strength, the atoms in the outermost four layers of the nanoribbons show obvious charge gain and loss. When the vertical electric field is applied to the hydrogenated nanoribbons, the energy gap changes are related to the period width. Their electrical properties realized the conversion between the semi-metal properties and the direct band gap semiconductor properties. Charge transfer occurs between the adjacent two layers of atoms. Under the same electric field strength, the amount of charge transfer increases from left to right along the direction of the width of the nanoribbon; at the same time, with the increase of the electric field strength, the amount of charge transfer also presents an increasing trend.

Structures and electronic properties of single-walled silicon nanotubes (6,m) under external electric field by SCC-DFTB calculations

In this work, using the self-consistent charge density functional tight-binding(SCC-DFTB) approach, we studied essential properties of SWSiNTs (6,m) and effects of perpendicular electronic field and strengths on electronic properties. After atomic relaxation, the structure of the tube changes obviously and different degrees of warping appear. The wall buckling distance is determined by the distance between outward and inward maximum values of the atom. The deviation of atomic radial displacement obviously affects the amount of atomic charge transfer, which increases with the increase of degree of buckling structure. The three primitive tubes are direct band gap semiconductors, among which the armchair tube has the highest binding energy and the most stable structure. As the applied electric field strength increases, the energy separation between adjacent subbands increases, causing a semiconductor-metal transition. The effect of electric field on the atomic charge redistribution in the tube is positively correlated with the warpage of the tube.

Molecular dynamics study of crystal lattice effect on mechanical properties of SiO2: A density functional tight binding investigation

In this study, molecular dynamics simulations (MD) based on quantum mechanical method in which the interactions were expressed by self-consistent charge density functional tight binding (SCC-DFTB) to investigate the mechanical properties of four different SiO2 structures. The Young's, shear and bulk modulus of systems are calculated and the results compared to experimental and other computational findings. We have observed that the hexagonal SiO2 exhibits more different mechanical behavior than other SiO2 structures because of its negative bulk modulus value. While the length of a-lattice parameters for four SiO2 crystal structures increase with the change of MD time, the length of the b and c-lattice vectors shortens. Moreover, it is analyzed the stress-strain behavior and yield points are determined from this curve of SiO2 structures. It is revealed that the plastic deformation occurs at higher stress for hexagonal SiO2 than other SiO2 structures because of its rigid solid property. These results can provide a reference for understanding the mechanical properties of various SiO2 crystal structures.

Effects of chiral index, vacancy defects and external electric field on the structures and electronic properties of DWSiNTs by SCC-DFTB calculations

As a new candidate material, silicon nanotubes (SiNTs) have been widely studied. However, various types of structural defects and external electric field are usually inescapability introduced in the experimental process of SiNTs synthesis. Structures, stability and electronic properties of the materials especially for double-walled silicon nanotubes (DWSiNTs) require to be considered. In this work, effects of vacancy defects and external electric field on properties of the geometrically structural optimization and electronic properties of DWSiNTs zigzag (3,0)@(7,0) and armchair (3,3)@(7,7) are studied via the self-consistent charge density functional tight binding (SCC-DFTB) method. The results of us show that the regular arrangement of the atoms, quantum molecular descriptors, distribution of charge, the degree of warping, stability, energy gap and Fermi energy levels intensely hinge on the chirality index of the tube and impacts of vacancy defects and electric field. Especially, the appearance of monovacancy and the change of vacancy density have the most significant effect on the band gap. For the pristine tubes, the charges transfer from the inside to the outside along the radial direction of the tube exhibiting an axisymmetric distribution. With the introduction of defects, the range of the charge transfer is broadened dramatically. The direction of charge transfer in the applied electric field is always opposite to the field direction. Our work may provide a new route to tune the electronic properties of DWSiNTs and opens a wider field of its application in nano-electronic devices.