First‐principles study of the TiN(111)/ZrN(111) interface

The TiN(111)/ZrN(111) interface was studied by first‐principles method to provide the theoretical basis for developing the TiN/ZrN coatings. Twelve geometry structures of TiN(111)/ZrN(111) interfaces were established. The calculated interfacial work of adhesion reveals that the N‐terminated TiN/N‐terminated ZrN interface with TL site shows the strongest stability. For this TiN(111)/ZrN(111) interface, the results of the partial density of state indicate that the chemical bonding at the interface appeals both ionic and covalent characteristic, which is same as that in the bulk materials. The partial density of states for Zr, Ti, and N atoms at the interface are very similar with those in the bulk, which reveals that the electronic structure transition at the interface is smooth. The results of charge density and charge density difference demonstrate that the lost charge of Ti atom is larger than that of Zr atom, indicating that TiN is more ionic than ZrN. Calculations of the work of fracture indicate that the mechanical failure of the ZrN(111)/TiN(111) interface will take place at the interface. Besides that, the calculation result of the TiN(111)/ZrN(111) interface implies that the TiZrN₂ phase might be formed at the interface because the contacting of the N―N bond is the most stable.     

First‐principles examination of low tolerance factor perovskites

Perovskites are generally formed in the non‐polar Pnma phase. The materials found in the polar subgroup of Pnma are not common. This article reports how perovskites having a low tolerance factor display ferroelectric instabilities in artificially constrained Pnma phase. The bond length distribution and the bond valence sum were analyzed to examine the origin of the ferroelectric behavior of low tolerance factor materials. However, the ground state structure of low tolerance perovskite is not Pnma phase, but either ilmenite (R ) or lithium niobate (R3c) phase. Here, epitaxial strain was used as a tuning parameter to stabilize the polar subgroup of Pnma. The rationalized principles from these studies will be valuable for designing new ferroelectric materials in the future.     

Interface of ZnS single sheet and substrates: a first‐principles study

Two‐dimensional materials have aroused great interests because of their unique properties not seen in the bulk counterparts. The interface of the ZnS single sheet and substrates are studied in this paper. Different from isolated ZnS single sheet, here in this study, the ZnS single sheet has a remarkable corrugation feature because of the interaction between the ZnS single sheet and the substrate. The top‐site Zn means an attractive reaction with the substrate while the top‐site S means repulsive. For ZnS single sheet/Si(111) interface, the symmetry of the interface does not decrease after geometry optimization because the two layers have a good lattice matching. For ZnS single sheet/Ag(111) interface, an unbalanced interaction (attractive or repulsive) between the ZnS single sheet (Zn or S atom) and Ag surface leads to remarkable corrugation of the ZnS single sheet and the symmetry of the interface decreases. Copyright © 2017 John Wiley & Sons, Ltd.     

First‐principles calculation of OH−/OH adsorption on gold nanoparticles

The OH^? and OH adsorption structures on Au₅₅ and Au₁₃ nanoparticles surfaces are analyzed using density functional theory. The most stable OH^? adsorption site of Au₅₅ and Au₁₃ nanoparticles is found to be the vertex top site followed by the (111)‐(100) edge bridge site. On the contrary, the stability order of OH adsorption is opposite to that of OH^?. The adsorption of OH^? is calculated to be weaker than that of OH, which shows different charge transfer and interactions with gold surface. Coadsorption on nanoparticles is studied to find that multiple OH^? species prefer the most stable sites of single OH^? adsorption. The hydrogen bonding between adsorbed OH^? on gold surface is a key factor in stabilizing the adsorbates on the Au surface. © 2015 Wiley Periodicals, Inc.     

First‐principles calculations of oxygen adsorption on the Ti3Al (0001) surface

Adsorption energies and density of states for O atoms adsorption on the Ti₃Al (0001) surface have been calculated using first‐principles calculations based on density functional theory. It is found that the order of O atom adsorption on the Ti₃Al (0001) surface is associated with the adsorption energy as well as the distance of O atoms because of the interaction. The adsorption energy mainly depends on the bond number and bond strength between O and Ti atoms, and the adsorption site with rich‐Ti surface (H_I and HCP_Al) is first priority. The adsorption energy decreases with the increase of the oxygen coverage because of the characteristics of the valence d‐orbitals of transition metals surface. Furthermore, the density of states indicates that the hybridization peak of O and Ti atoms is mainly from the contribution of Ti 3d‐ and O 2p‐orbitals, and the hybridization peak of O and Al atoms from the contribution of Al 2p‐ and O 2p‐orbitals. Copyright © 2016 John Wiley & Sons, Ltd.     

First‐principles study of the (001) surface of cubic PbTiO3

We present first‐principles calculations on the (001) surfaces of cubic PbTiO₃ with PbO and TiO₂ terminations. The cleavage energy, surface energy, surface grand potential, surface relaxation and surface electronic structure have been investigated by using the projector‐augmented wave method under generalized gradient approximation (GGA). The results show that surface energy of a TiO₂‐terminated surface is a little lower than that of a PbO‐terminated one, thus allowing both terminations to coexist. The PbO‐termination is stable in O‐ and Pb‐rich environments, while on the contrary, the TiO₂‐termination is stable in O‐ and Pb‐poor conditions. In addition, the surface rumpling S of a PbO‐terminated surface is slightly larger than that of a TiO₂‐terminated one. The relaxations dominantly take place on the outermost three layers, and an oscillatory (? + ?) damping (|Δd₁₂ | > | Δd₂₃ | > | Δd₃₄|) relaxation phenomenon appears for both terminations. The band gaps of both PbO‐ and TiO₂‐terminations are slightly lower than that of the bulk. Moreover, the DOS curves of each layer show that for the TiO₂‐termination, the top of the valence band of the first and third TiO₂ layers moves toward Fermi level. Copyright © 2008 John Wiley & Sons, Ltd.     

First‐principles calculations of the stability and electronic properties of the PbTiO3 (110) polar surface

The structural and electronic properties of five terminations of cubic lead titanate (PbTiO₃) (110) polar surface were investigated by first‐principles total‐energy calculations using a periodic slab model. On the PbTiO termination, an anomalous filling of conduction band was observed, whereas on the O₂ termination, two surface oxygen atoms formed a peroxo group, demonstrating that the electronic structures of the two stoichiometric terminations undergo significant changes with respect to bulk materials. However, for the three nonstoichiometric TiO‐, Pb‐, and O‐terminated surfaces, their electronic structures are very similar to bulk. Charge redistribution results for the five terminations confirmed that electronic structure and surface composition changes are responsible for their polarity compensation. However, which mechanism actually dominates the stabilization process depends upon energetic considerations. A thermodynamic stability diagram suggested that the two stoichiometric terminations are unstable; however, the three nonstoichiometric terminations can be stabilized in some given regions. Furthermore, this study indicates that the very different stabilities and surface states filling behaviors of the PbTiO₃ (110) polar surface with respect to SrTiO₃ and BaTiO₃ ones seem to originate from the partially covalent characteristics of Pb O pairs. © 2008 Wiley Periodicals, Inc. J Comput Chem 2009     

Structural,electronic, and magnetic properties of 3d transition metal doped GaN nanosheet: A first‐principles study

We have performed the first‐principles calculations on the structural, electronic, and magnetic properties of 3d transition‐metal? (Cr, Mn, Fe, Co, and Ni) atoms doped 2D GaN nanosheet. The results show that 3d TM atom substituting one Ga leads to a structural reconstruction around the 3d TM impurity compared to the pristine GaN nanosheet. The doping of TM atom can induce magnetic moments, which are mainly located on the 3d TM atom and its nearest‐neighbor N atoms. It is found that Mn‐ and Ni‐doped GaN nanosheet with 100% spin polarization characters seem to be good candidates for spintronic applications. When two Ga atoms are substituted by two TM dopants, the ferromagnetic (FM) ordering becomes energetically more favorable for Cr‐, Mn‐, and Ni‐doped GaN nanosheet with different distances of two TM atoms. On the contrary, the antiferromagnetic (AFM) ordering is energetically more favorable for Fe‐doped GaN nanosheet. In addition, our GGA + U calculations show the similar results with GGA calculations. © 2016 Wiley Periodicals, Inc.     

Adhesion,atomic structure,and bonding variation at TiN/VN interface by chemical segregation

Introduction of alloying elements often alters properties of materials. In the technologically significant multilayered superlattice coatings, interfaces are known to play a key role in the deformation mechanisms, especially in the phenomenon of interface‐induced superhardness at nanoscale. Here, we elucidate, by first‐principles calculations, atomic structure of TiN/VN interface and its relationship to adhesion upon introducing Cr, Mo, Ta, Y, Al, Nb, Zr, and Sc, the very commonly occurring alloying elements in the coating. We find that the elements Cr, Mo, Ta, Y weaken substantially interfacial adhesion, whereas the others modify adhesion only slightly. The bond length, charge transfer, and interactions between atoms at interface are found to be the key factors to understanding the origin of shift in properties in the coatings with the chemical alloying. Using several methods of analysis, we have clarified electronic mechanism behind the variation induced by alloying elements and determined the interfacial bonding nature to be mainly ionic with a certain degree of covalency. The theoretical calculations presented provide insight into the complex electronic properties of the TiN/VN interfaces with alloying elements. Our findings help enhance performances of the multilayered coatings for wide‐ranging applications. Copyright © 2012 John Wiley & Sons, Ltd.     

The interface effect on the lithiation of silicon/graphene composites: The first principles study

To reveal the interaction mechanism between lithium (Li) and silicon/graphene (Si/Gra) interface at the atomic scale, it was calculated that the energy band structure, density of states, charge transfer, radial distribution function and Li diffusion coefficient based on the first principles. The results indicated that the volume expansion of Si was effectively limited by the Si/Gra interface during Li insertion. There appeared the interface effect of Si/Gra on the combination of Li and Si atoms, according to the longer Li-C (2.9 Å) and the larger electron cloud near the Li atom at the Si/Gra interface. The better diffusion channel for Li atoms was constructed at the Si/Gra interface, due to the lower diffusion energy barrier (0.42–0.44 eV) and higher diffusion coefficient (D_Li = 0.784 × 10⁻⁴ cm²/s) for Li⁺ diffusion.     

First‐Principles Study on Doping of SnSe2 Monolayers

Doping is a vitally important technique that can be used to modulate the properties of two‐dimensional materials. In this work, by using first‐principles density functional calculations, we investigated the electrical properties of SnSe₂ monolayers by p‐type/n‐type and isoelectronic doping. Substitution at Sn/Se sites was found to be easy if the monolayer was grown under Sn‐/Se‐poor conditions. Substitutions at Sn sites with metallic atoms (e.g. Ga, Ge, In, Bi, Sb, Pb) resulted in positive substitution energies, which indicated that they were not effective doping candidates. For substitutions at Se sites with nonmetallic atoms, no promising candidates were found for p‐type doping (e.g., N, P, As). Among these, N and As showed positive substitution energies. Although P had a negative substitution energy under Sn‐rich conditions, it introduced trap states within the band gap. For n‐type doping (e.g., F, Cl, Br), all the calculated substitution energies were negative under both Sn‐ and Se‐rich conditions. Br was proven to be a promising candidate, because the impurity introduced a shallow donor level. Finally, for isoelectronic doping (e.g., O, S, Te), the intrinsic semiconducting features of the SnSe₂ monolayer did not change, and the contribution from the impurity to the states near the band edge increased with the atomic number.     

First‐principles study of molecular hydrogen dissociation on doped Al12X (X = B,Al, C,Si, P,Mg, and Ca) clusters

Inspired by the concept of superatom via substitutionally doping an Al₁₃ magic cluster, we investigated the H₂ molecule dissociation on the doped icosahedral Al₁₂X (X = B, Al, C, Si, P, Mg, and Ca) clusters by means of density functional theory. The computed reaction energies and activation barriers show that the concept of superatom is still valid for the catalysis behavior of doped metal clusters. The hydrogen dissociation behavior on metal clusters characterized by the activation barrier and reaction energy can be tuned by controllable doping. Thus, doped Al₁₂X clusters might serve as highly efficient and low‐cost catalysts for hydrogen dissociation. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2009     

TiS2 and ZrS2 single‐ and double‐wall nanotubes: First‐principles study

Hybrid density functional theory has been applied for investigations of the electronic and atomic structure of bulk phases, nanolayers, and nanotubes based on titanium and zirconium disulfides. Calculations have been performed on the basis of the localized atomic functions by means of the CRYSTAL‐2009 computer code. The full optimization of all atomic positions in the regarded systems has been made to study the atomic relaxation and to determine the most favorable structures. The different layered and isotropic bulk phases have been considered as the possible precursors of the nanotubes. Calculations on single‐walled TiS₂ and ZrS₂ nanotubes confirmed that the nanotubes obtained by rolling up the hexagonal crystalline layers with octahedral 1T morphology are the most stable. The strain energy of TiS₂ and ZrS₂ nanotubes is small, does not depend on the tube chirality, and approximately obeys to D^–2 law (D is nanotube diameter) of the classical elasticity theory. It is greater than the strain energy of the similar TiO₂ and ZrO₂ nanotubes; however, the formation energy of the disulfide nanotubes is considerably less than the formation energy of the dioxide nanotubes. The distance and interaction energy between the single‐wall components of the double‐wall nanotubes is proved to be close to the distance and interaction energy between layers in the layered crystals. Analysis of the relaxed nanotube shape using radial coordinate of the metal atoms demonstrates a small but noticeable deviation from completely cylindrical cross‐section of the external walls in the armchair‐like double‐wall nanotubes. © 2013 Wiley Periodicals, Inc.     

Deformation of single‐walled carbon nanotubes by interaction with graphene: A first‐principles study

The interaction between single‐walled carbon nanotubes (SWNTs) and graphene were studied with first‐principles calculations. Both SWNTs and single‐layer graphene (SLG) or double‐layer graphene (DLG) display more remarkable deformations with the increase of SWNT diameter, which implies a stronger interaction between SWNTs and graphene. Besides, in DLG, deformation of the upper‐layer graphene is less than in SLG. Zigzag SWNTs show stronger interactions with SLG than armchair SWNTs, whereas the order is reversed for DLG, which can be interpreted by the mechanical properties of SWNTs and graphene. Density of states and band structures were also studied, and it was found that the interaction between a SWNT and graphene is not strong enough to bring about obvious influence on the electronic structures of SWNTs. © 2015 Wiley Periodicals, Inc.     

Effect of spin polarization for hydrogen adsorbed on Si(111)(1×1) surface: First‐principles calculations

The role of spin polarization on adsorption of atomic and molecular hydrogen on Si(111)(1×1) surface is examined by comparing the results of the local spin density approximation (LSD) and those of the local density approximation (LDA). A large improvement of the adsorption energies (around 0.8 eV/H) was found for the H atom adsorbed on Si(111)(1×1) surface. The inclusion of spin polarization reduces the overbinding between the H atom and the silicon surface and its effect is much more pronounced when the H atom is far away from the surface. Despite of the large changes in the adsorption energies, the main character of the potential energy surface of the H atom on Si(111)(1×1) surface is retained. An opposite effect is found in the charge‐density‐transfer map of LSD results as compared to LDA results for the H atom approaching the surface through the H3 path, in which the H atom loses electrons rather than gains electrons from the surface. The fact that the H atom tends to lose electrons in the silicon bulk has already been reported by the experimental studies for the behavior of the H atom in the p‐type silicon. For the molecular hydrogen on Si(111)(1×1) surface, the effect of the spin polarization is so small that it can be neglected. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 47–55, 2000     

Interactions between hydrogenated diamond surface and adsorbates with different concentration of NO2 molecules: A first‐principles study

To elucidate the effects of NO₂ and H₂O molecules on the surface conductivity of hydrogenated diamond film, models of various adsorbates containing different molecular ratio of NO₂ and H₂O on hydrogenated diamond (100) surfaces were constructed. The adsorption energies, equilibrium geometries of adsorbates, density of states, and atomic Mulliken populations were studied by using first‐principles method. The results showed that H₂O molecule in the adsorbate could weaken the interactions between the adsorbates and hydrogenated diamond surface significantly. Compared with H₂O molecule, NO₂ molecule relaxes more dramatically when adsorbed on hydrogenated diamond surface. In addition, density of states for C(100):H–2NO₂, C(100):H–NO₂, and C(100):H–NO₂ + H₂O systems are very similar to each other, which indicates an obvious peak at valence band maximum level for all the three samples. It can be attributed to mainly single occupied molecule orbital of NO₂ molecule and slightly C–H bond of C(100):H substrate. When the adsorbates contain one NO₂ and two H₂O molecules, the peak shifts slightly into valence band, but its intensity increases significantly. All the samples exhibit p‐type surface conductivity when adsorbed with pure NO₂ molecules, and the surface conductivity remains as H₂O molecules added into the NO₂ adsorbate layer. However, for oxygenated diamond surface, very week interactions generate between diamond surface and various adsorbates. All the oxygenated diamond (100) surfaces with various adsorbates containing different NO₂ and H₂O molecules on it exhibit an insulating property.     

Characterization of ultrafast processes at metal/solution interfaces: Towards femtoelectrochemistry

The essential part of electrochemistry is charge transfer. To understand this process in great detail, one needs to probe the relevant kinetics and dynamics on time scales spanning from femtoseconds to seconds or even longer. Although a conventional electrochemical detection scheme is sufficient for nanosecond or slower processes, it does not offer high enough time resolution for probing ultrafast processes, such as solvent reorganization, electron tunneling, and surface isomerization, that occur on faster, for example picosecond or femtosecond, timescales. These are indispensable parameters in the advanced charge transfer theories. In this review, some recent studies using ultrashort lasers to explore the ultrafast dynamics at the metal/solution interface are reviewed. The focus is on optical pump-probe and optical pump-push with electrochemical probe schemes. The connection of these studies with conventional electrochemistry and the limitations of these detection schemes are discussed.     

First-principles calculations of the structural,elastic and electronic properties of MNxC1−x (M = Ti,Zr, Hf; 0 ≤ x ≤ 1) carbonitrides at ambient and elevated hydrostatic pressure

The structural, electronic, and elastic properties of three mixed transition metal carbonitrides TiN_xC_1−x, ZrN_xC_1−x, and HfN_xC_1−x (0 ≤ x ≤ 1) with the rock-salt structure were calculated at ambient and elevated up to 50 GPa hydrostatic pressures in the framework of the density functional theory methods. The lattice constants, densities, and bulk moduli of the considered compounds were shown to behave as linear functions of the nitrogen concentration x. The obtained linear dependencies of all these parameters allow for getting their estimates at any value of x in the range from 0 to 1. Gradual enhancement of the ionicity of the chemical bonds with gradual replacement of carbon by nitrogen was demonstrated by calculating the bond orders and electron density difference distributions.