First-principles investigation of cohesive energy and electronic structure in vanadium phosphides

First-principles calculations based on the density-functional theory were employed to study the crystal structure of vanadium phosphide compounds,such as V3P,V2P,VP,VP2 and VP4. Cohesive energy of five types of vanadium phosphide compounds was calculated to assess their structural stability. The charge density distribution and densities of states of vanadium phosphides were discussed to study further their electronic structures. The results show that the structure of metal-rich compounds is considerably more stable than the phosphorus-rich compositions,and covalent bond exists between the V and P atoms of V3P,V2P,VP,VP2 and VP4.

Higher Order Multipole Potentials and Electrostatic Screening Effects on Cohesive Energy and Bulk Modulus of Metallic Nanoparticles

Higher order rnultipole potentials and electrostatic screening effects are introduced to incorporate the dan gling bonds on the surface of a metallic nanopaticle and to modify the coulornb like potential energy terms, respectively. The total interaction energy function for any rnetallic nanoparticle is represented in terms of two- and three-body potentials. The two-body part is described by dipole-dipole interaction potential, and in the three-body part, triple-dipole （DDD） and dipole-dipole-quadrupole （DDQ） terrns are included. The size-dependent cohesive energy and bulk modulus are observed to decrease with decreasing sizes, a result which is in good agreement with the experimental values of Mo and W nanoparticles.

Equation of state for solids considering cohesive energy and anharmonic effect and its application to MgO

A simple equation of state （EOS） in wide ranges of pressure and temperature is constructed within the MieGruneisen Debye framework. Instead of the popular Birch-Murnaghan and Vinet EOS, we employ a five-parameter cold energy expression to represent the static EOS term, which can correctly produce cohesive energy without any spurious oscillations in the extreme compression and expansion regions, We developed a Pade approximation-based analytic Debye quasiharmonic model with high accuracy which improves the performance of EOS in the low temperature region. The anharmonic effect is taken into account by using a semi-empirical approach. Its reasonability is verified by the fact that the total thermal pressure tends to the lowest-order anharmonic expansion in the literature at low temperature, and tends to ideal-gas limitation at high temperature, which is physically correct. Besides, based on this approach, the anharmonic thermal pressure can be expressed in the Griineisen form, which is convenient for applications. The proposed EOS is used to study the thermodynamic properties of MgO including static and shock compression conditions, and the results are very satisfactory as compared with the experimental data.

Five-parameter equation of state for solids correctly incorporating cohesive energy data

A five-parameter equation of state （EOS） is proposed to correctly incorporate the cohesive energy data in it without physically incorrect oscillations. The proposed EOS is applied to 10 selected metals. It is shown that the calculated compression curves are in good accordance with the experimental data. The values of the bulk modulus and its derivative with respect to pressure extracted from the proposed EOS remain almost unchanged while the data range used is varied.

Electronic Structures and Properties of V, Nb and Ta Metals

The electronic structures of pure V, Nb and Ta metals with bcc structure were determined by one atom (OA) theory. According to the electronic structures of these metals, their potential curves, cohesive energies, lattice parameters, elasticity and the dependence of linear thermal expansion coefficients on temperature were calculated. The electronic structures and characteristic properties of these metals with fcc and hcp structures and liquid states were studied.

Structures and Properties of Sc and Y Metals

The electronic structures of pure Sc and Y metals with hcp structure have been determined by one atom (OA) theory, which are [Ar](3d c) 1.331 5 (4s c) 0.905 0 (4s f) 0.763 5 and [Kr](4d c) 1.293 0 (5s c) 0.947 0 (5s f) 0.760 0 . According to their electronic structure, their potential curves, cohesive energies, lattice constants, elasticity and the temperature dependence of linear thermal expansion coefficients have been calculated. The electronic structures and characteristic properties of these metals with bcc structures and primary liquids have also been studied, which has supplied the structural parameters and property parameters of Sc and Y with different crystal structures and also supplied a series of complete data for the theoretical design of Sc and Y based materials.

Electronic structures and properties of Ti, Zr and Hf metals

The electronic structures of pure Ti, Zr and Hf metals with hcp structure were determined by one atom (OA) theory. According to the electronic structures of these metals,their potential curves, cohesive energies, lattice constants, elasticities and the temperature dependence of linear thermal expansion coefficients were calculated. The electronic structures and characteristic properties of these metals with bcc and fcc structures and liquids were also studied. The results show that the electronic structures of Ti, Zr and Hf metals are respectively [Ar](3d n) 0.481 0 (3d c) 2.085 7 (4s c) 1.000 0 (4s f) 0.433 3 , [Kr](4d n) 0.396 8 (4d c) 2.142 8 (5s c) 1.262 0 (5s f) 0.198 4 , [Xe](5d n) 0.368 0 (5d c) 2.041 4 (6s c) 1.406 6 (6s f) 0.184 0 . It is explained why the pure Ti, Zr and Hf metals with hcp and bcc structures can exist naturally, while those with fcc structure can not.

ELECTRONIC STRUCTURE AND PROPERTIES OF Au METAL

Using the new developed valence bond theory of metals,the electronic structure,crystal structure and physical properties of Au metal have been systematically analysed.It has been determined that its electronic structure is(5d_(n))^(4.65)(5d_(c))^(4.71)(6s_(c))^(0.62)(6s_(f))^(1.02).According to this electronic structure,lattice constant,cohesive energy.potential curve,bulk modulus and temperature dependence of liner thermal expansion coeCHcient have been calculated.The theoretical values of properties are all in good agreement with experimental results.This electronic structure has been verified in part by linear rigorous cellular method of band theory.It shows that the valence bond theory has been reached perfectly.

First Principle Calculation of NbC Precipitation Competition between TiC Particle and Ferrite Matrix

The electronic structure, cohesive energy and interfacial energy of ferrite（100）/NbC（100） and TiC（100）/NbC（100） interfaces have been investigated by the first-principles calculation. Moreover, the heterogeneous nuclei mechanism of NbC particle was also analyzed. The results showed that the stacking sequences have a great influence on the cohesive energy and equilibrium interfacial separation of the abovementioned interfaces. Compared with C-terminated interfaces, the cohesive energy of Nb-terminated ones is lower while the equilibrium interface distance is larger. Among the two C-terminated interface structures, the interfacial energy between the NbC and ferrite is 4.54 J/m^2, which is larger than that of NbC/TiC interface（1.80 J/m^2）. Therefore, NbC particles prefer heterogeneous nucleation on TiC particles surface rather than the ferrite matrix, which agrees well with the experimental result.

Yuan Jianmin Zhao Yijun Zhang Zhijie (At.Mol.Phys.and Physical Mechanics Research Center,National Univ of Defense Tech.,Changsha,Hunan,P.R.China)

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CONFORMATION AND CHAIN PACKING STRUCTURES OF POLY (ρ-PHENYLEN BENZOBISTHIAZOLE) BY MOLECULAR SIMULATION

The conformation, the chain packing stabilization and the unit cell modeling of poly(p-phenylene benzobisthiazole) have been investigated by using molecular simulation techniquein the present work. A coupling behaviour of σ-bond rotations at either side of the pheny-lene ring or the heterocyclic ring was found surely to exceed a length of the repeat unit ofthe polymer chain. For a single chain model, the stable torsion angle of the repeat resultedat 14°. In the crystalline cell minimization, the dihedral angle along the polymer chaincould even be stabilized in various values. It therefore indicates that the intermolecularinteraction does play a considerable role for this polymer forming the conformation. Ac-cording to cohesive energies calculated for these unit cell models, the torsion angle in themost stable crystalline cell is 0°. When the chains packing together, there exist so manyenergy stable wells along the chain axis 0.35--0.36nm apart from neighbouring chains.Most of the unit cells have quite closed cohesive energies. These factors thus cause thedifficulty of forming an unique perfect crystalline structure of the polymer. The presentstudy suggested a number of reasonable unit cells, and the most stable crystalline structurefor this polymer that is monoclinic, non-primitive unit cell.

Relaxation of Small Molecules：an ab initio Study

Using an ab initio total energy and force method, we have relaxed several group IV and group V elementalclusters, in detail the arsenic and antimony dimers, silicon, phosphorus, arsenic and antimony tetramers. The obtainedbond lengths and cohesive energies are more accurate than other calculating methods, and in excellent agreement withthe experimental results.

Characteristics and mechanism of abrasive wear for thermoplastic polymers

Abrasive wear characteristics of polyethylene, polystyrene,polymethylmethacrylate, nylon 1010 and polyvinyl chloride were investigated. The volume relativewear resistance coefficients of these thermoplastic polymers are 18%-35% (hardened and lowtemperature tempered steel 45 was used as a comparing material), and have a linear correlation withsquare roots of their cohesive energy densities. The coefficients of linear correlation is 0.949.Wear morphologies were observed by scanning electron microscope (SEM). Main wear mechanism of thethermoplastic polymers includes brittle breaking for the hard and brittle polymers & plowing andfatiguing for the soft and tough ones.

Transport Properties of Ferrite Perovskite Material

Transport properties of LaFeO3 in the temperature range of 2 K 〈 T 〈 300 K have been explored for the first time using interaction potential developed by the author and found that our computed results on transport properties follow the same trend as that of available experimental values. These are scientifically and technologically important materials with orthorhombic perovskite-like structure and space group Pbnm. Lanthanum ferrite, LaFeO3 is semiconducting and antiferrom agnetically ordered at zero. The thermodynamics of perovskite-type or related materials of potential use in, e.g., solid oxide fuel cells have been studied to a rather limited extent only.

Molecular dynamics study on the relationships of modeling,structural and energy properties with sensitivity for RDX-based PBXs

In this paper,a primary model is established for MD(molecular dynamics) simulation for the PBXs(polymer-bonded explosives) with RDX(cyclotrimethylene trinitramine) as base explosive and PS as polymer binder.A series of results from the MD simulation are compared between two PBX models,which are represented by PBX1 and PBX2,respectively,including one PS molecular chain having 46 repeating units and two PS molecular chains with each having 23 repeating units.It has been found that their structural,interaction energy and mechanical properties are basically consistent between the two models.A systematic MD study for the PBX2 is performed under NPT conditions at five different temperatures,i.e.,195 K,245 K,295 K,345 K,and 395 K.We have found that with the temperature increase,the maximum bond length(L max) of RDX N N trigger bond increases,and the interaction energy(E N-N) between two N atoms of the N-N trigger bond and the cohesive energy density(CED) decrease.These phenomena agree with the experimental fact that the PBX becomes more sensitive as the temperature increases.Therefore,we propose to use the maximum bond length L max of the trigger bond of the easily decomposed and exploded component and the interaction energy E N-N of the two relevant atoms as theoretical criteria to judge or predict the relative degree of heat and impact sensitivity for the energetic composites such as PBXs and solid propellants.

Electronic structure of Ag-Cu alloys

According to the correlativity between energy, volume and electronic structure of characteristic crystals and bound conditions of OA theory, the Gibbs energy function, atomic volume function and electronic structure of Ag Cu alloys have been determined. Then the electronic structure and properties of disordered alloys with any composition and ordered alloys with any ordering degree can be calculated. The number of d c covalent electrons in the states of Ag characteristic atoms decreases with the increase of Cu atoms in the nearest neighbouring shell. The number of d c covalent electrons in the states of Cu characteristic atoms decreases with the increase of Ag atoms in the nearest neighbouring shell. Such changes lead to the tendencies of atomic segregation and partition into two phases in the Ag Cu system.

Kinetically-Induced Hexagonality in Chemically Grown Silicon Nanowires

Various silicon crystal structures with different atomic arrangements from that of diamond have been observed in chemically synthesized nanowires.The structures are typified by mixed stacking mismatches of closely packed Si dimers.Instead of viewing them as defects,we define the concept of hexagonality and describe these structures as Si polymorphs.The small transverse dimensions of a nanowire make this approach meaningful.Unique among the polymorphs are cubic symmetry diamond and hexagonal symmetry wurtzite structures.Electron diffraction studies conducted with Au as an internal reference unambiguously confirm the existence of the hexagonal symmetry Si nanowires.Cohesive energy calculations suggest that the wurtzite polymorph is the least stable and the diamond polymorph is the most stable.Cohesive energies of intermediate polymorphs follow a linear trend with respect to their structural hexagonality.We identify the driving force in the polymorph formations as the growth kinetics.Fast longitudinal elongation during the growth freezes stacking mismatches and thus leads to a variety of Si polymorphs.The results are expected to shed new light on the importance of growth kinetics in nanomaterial syntheses and may open up ways to produce structures that are uncommon in bulk materials.

Interface adhesion properties characterization of sulfide electrode materials by the combination of BOLS and XPS

Although sulfide electrode materials in lithium battery systems have been intensively investigated due to their low-cost, high theoretical specific capacity, and energy density, there are few studies fousing on the adhesion properties, including the physical origin of hetero-coordination resolved interface relaxation, binding energy and the energetic behavior, and even the accurate quantitative information. In this paper, we present an approach for quantifying the interface adhesion properties of sulfide electrode materials resolved by the combination of bond order-length-strength theory(BOLS) and X-ray photoelectron spectroscopy(XPS), which has enabled clarification of the interface adhesion nature. The results show that the Cu 2p, Fe 2p, and S 2p electrons of Cu S and FeS_(2) compounds shift negatively due to the charge polarization of the conduction electrons of the heteroatoms, while Mo 3d, Sn 3d electrons of Mo S2 and Sn S2 and the C 1 s and S 2p electrons of CS compound shift positively due to the quantum trapping. It is noted that the exact interface adhesion energies of Cu S is 3.42 J m^(-2), which is consistent with the calculation result. The approach can not only clarify the origin of the interface adhesion properties of sulfide electrode materials,but also derive their quantification information from atomistic sites.