Mechanisms of formation of near-edge fine structure of <Emphasis Type="Italic">K</Emphasis> X-ray absorption spectra of metallic Cu,Ni, Co (HCP and FCC phases), and Cr

The K X-ray absorption near-edge fine structure spectra of metallic Cu, Ni, Co (hexagonal close-packed and face-centered cubic phases), and Cr have been studied. The experimental spectrum of cobalt has been measured in the high-temperature face-centered cubic phase. The calculations have been performed by the full multiple scattering method in the cluster approximation using the semiempirical muffin-tin potential. The spectra have been calculated for clusters containing from 13 to 935 atoms. It has been demonstrated that the spectra cease to depend on the cluster size for clusters containing about 400 atoms. It has been established that the intensity ratio of two peaks located at the fundamental edge of all the spectra under investigation sharply changes with a variation in the atomic potential strength. The mechanisms responsible for the formation of the near-edge structure of the spectra have been revealed using the results of the model calculations. The studies resulted in good agreement of the calculated spectra with the experiment.     

Simulation of the processes of structuring of copper nanoclusters in terms of the tight-binding potential

The processes of melting and crystallization of copper nanoclusters with a radius ranging from 0.69 to 3.05 nm have been investigated using the molecular dynamics simulation. The performed simulation has shown that the melting begins with the surface of the cluster. Another feature of this phase transition is that it occurs in a temperature range where the liquid and solid phases can coexist. However, it is found that, for small copper clusters, the melting and crystallization temperatures coincide with each other. Moreover, it is established that the parent face-centered cubic structure of these small clusters (N < 150 atoms) transforms into a structure with fivefold symmetry even at temperatures of the order of 150–170 K. The behavior of some thermodynamic characteristics of copper nanoclusters is investigated in the vicinity of the solid-liquid phase transition. Analysis of the data obtained has revealed a number of regularities that are in agreement with the results of analytical calculations. In particular, the melting and crystallization temperatures of copper nanoparticles are linear functions of N ^?1/3. However, the melting heat ΔH _m and the melting entropy ΔS _m vary in a more complex manner. It is noted that the formation of a cluster structure depends on the conditions used for cooling from the liquid phase. Slow cooling results predominantly in the formation of a face-centered cubic phase, whereas rapid cooling in the majority of cases leads to the formation of an icosahedral modification. Therefore, the simulation performed has demonstrated the possibility of controlling the formation of a structure of copper nanoclusters during crystallization.     

Structural transitions in small nickel clusters

The processes of a thermal impact on Ni nanoclusters with a radius of up to 0.8 nm have been studied by means of molecular dynamics with the use of a tight-binding potential. The simulation indicates that the structural transition from the initial fcc phase to the icosahedral modification occurs under the influence of temperature. The transition temperature is shifted towards the cluster melting temperature with an increase in the cluster size. A similar behavior has been observed for copper and gold nanoparticles. A conclusion has been drawn that 200–250 atoms is presumably the limiting size of a metallic cluster, below which the initial fcc modification cannot be kept under realistic industrial conditions. The adequacy of the results is checked in the computer experiments with Lennard-Jones nanoparticles. The results for the Lennard-Jones and metallic nanoparticles have been shown to agree with each other.     

Diffusion in a system of impurity centers with dipole-dipole hopping rates

Random walks in disordered media with dipole-dipole transition rates are considered. The long-time asymptotics of the process are investigated on the basis of a new numerical simulation method, which includes periodic continuation of the system without periodic continuation of the initial condition. It is shown that the long-time asymptotics have a diffusive character. The concentration dependence of the diffusion coefficient for simple cubic and face-centered cubic lattices is studied. Zh. éksp. Teor. Fiz. 114, 2166–2181 (December 1998)     

Phase transition and mechanical properties of tungsten nanomaterials from molecular dynamic simulation

Molecular dynamic simulation is used to systematically find out the effects of the size and shape of nanoparticles on phase transition and mechanical properties of W nanomaterials. It is revealed that the body-centered cubic (BCC) to face-centered cubic (FCC) phase transition could only happen in cubic nanoparticles of W, instead of the shapes of sphere, octahedron, and rhombic dodecahedron, and that the critical number to trigger the phase transition is 5374 atoms. Simulation also shows that the FCC nanocrystalline W should be prevented due to its much lower tensile strength than its BCC counterpart and that the octahedral and rhombic dodecahedral nanoparticles of W, rather than the cubic nanoparticles, should be preferred in terms of phase transition and mechanical properties. The derived results are discussed extensively through comparing with available observations in the literature to provide a deep understanding of W nanomaterials.     

Statistical theory of thermodynamic stability of crystalline phases

The equation of state of a face-centered cubic phase has been quantitatively analyzed in terms of the statistical theory of crystals. It has been shown that, for xenon at room temperature, the pressure equal to 1.5 GPa determines the instability point where the condition of the positive bulk modulus of a face-centered cubic crystal is violated. A “universal line” bounding the thermodynamic stability region of the face-centered cubic phase of van der Waals crystals has been constructed. An analysis of the data available in the literature allows the conclusion that the revealed transition of face-centered cubic xenon to the martensitic phase at a pressure of 1.5 GPa and a temperature of 300 K can be considered a manifestation of the predicted instability. In this respect, it is important to perform detailed experiments on polymorphic transformations of real xenon (and also krypton). Another aspect of the proposed theory is that it provides a means for quantitatively predicting the characteristics of the so-called “cold” (at negative pressures) melting, which recently has become accessible for experimental observation.     

Direct measurement of microstructural avalanches during the martensitic transition of cobalt using coherent x-ray scattering

Heterogeneous microscale dynamics in the martensitic phase transition of cobalt is investigated with real-time x-ray scattering. During the transformation of the high-temperature face-centered cubic phase to the low-temperature hexagonal close-packed phase, the structure factor evolution suggests that an initial rapid local transformation is followed by a slower period during which strain relaxes. Coherent x-ray scattering measurements performed during the latter part of the transformation show that the kinetics is dominated by discontinuous sudden changes-avalanches. The spatial size of observed avalanches varies widely, from 100 nm to 10 μm, the size of the x-ray beam. An empirical avalanche amplitude quantifies this behavior, exhibiting a power-law distribution. The avalanche rate decreases with inverse time since the onset of the transformation.     

Structural phase transition in a large cluster

The effect of a phase transition between structures in a large cluster with a pair interatomic interaction on the thermodynamic parameters of the cluster is analyzed. The statistical parameters of a cluster consisting of 923 atoms are determined for an icosahedron and a face-centered cubic (fcc) structure. The specific heat and entropy of this cluster are calculated in the case when the transition between the icosahedron and fcc structures has the greatest effect on these parameters, so that at zero temperature this cluster has the structure of an icosahedron, and as the temperature increases to the melting point it assumes an fcc structure. Even with this, the contribution of the excitations of the atomic configurations to the thermodynamic parameters of a cluster is small compared with the excitation of vibrations in the cluster. The contribution of a configurational excitation in the thermodynamic parameters of a cluster becomes substantial for the liquid state of clusters.     

On the prospects of preparing fullerites from small and large fullerenes

The evolution of the properties of face-centered cubic fullerites with a variation in the number (nc) of carbon atoms in a C_nc fullerene molecule (15 ≤ nc ≤ 147) is investigated using the dependence of the parameters of the interfullerene interaction in face-centered cubic fullerites on the mass of the C_nc fullerene molecule. It is demonstrated that, for nc < 20, the face-centered cubic fullerites become unstable because such light small fullerene molecules cannot be kept by weak van der Waals forces. For nc ≥ 110, the fullerites have anomalously low surface energies, which should lead to fragmentation of nanoclusters composed of large hollow spherical molecules C_nc. The inference is made that the range 30 < nc < 100 is optimum for the formation of stable face-centered cubic fullerites.     

Features of the optical absorption of crystals of the fullerene C60 in the region of the orientational phase transition

The absorption coefficient of perfect single crystals of the fullerene C₆₀ is measured in the energy range 1.6–2.1 eV at temperatures from 4.2 to 300 K. An absorption fine structure is discovered in the and is assigned to electronic and vibronic transitions with the production of free excitons and excitons localized on structural defects. It is shown that in the region of the structural phase transition from a face-centered cubic structure to a simple cubic structure the absorption coefficient undergoes a jump, which is associated with an energy shift of the free exciton line toward lower energies. It is discovered that spatial inhomogeneity, which is associated with the growth of the new phase from a finite number of nuclei, appears in the crystal at the time of this transition. Zh. éksp. Teor. Fiz. 114, 2211–2224 (December 1998)     

Homologous distortion of the aluminum crystal structure under laser radiation

It was shown by X-ray diffraction that the aluminum crystal structure is distorted under conditions of nonequilibrium laser heating, which appears in lowering the lattice symmetry. A method for describing the observed distortions, based on the transition to a new unit cell, was proposed. It was shown that the distorted aluminum crystal structure can be described using the transition from the face-centered cubic cell to the monoclinic body-centered cell. The parameters of the aluminum unit cell after laser irradiation were determined as a = 0.2870 nm, b = 0.2860 nm, c = 0.4060 nm, and β = 90.013° (for the axes of the monoclinic body-centered lattice).     

Molecular dynamics investigation of the size effect upon the β → α transformation in Zr nanocrystals

The stability of the β phase in cubic zirconium nanoparticles has been calculated as a function of the size r (r varies in the range from 2.5 to 11.5 nm) by the molecular dynamics method with the many-body interatomic interaction potential obtained within the embedded-atom model. It has been demonstrated that the temperature T _k at which the cubic cluster of body-centered cubic zirconium becomes structurally unstable depends nonlinearly on the particle size. The curve T _k (r) exhibits a pronounced maximum in the range r ≈ 4.3−4.7 nm. It has been established that the mechanism of the structural transition from the body-centered cubic phase to the hexagonal close-packed phase depends substantially on the particle size. For particles with sizes in the range from 2.5 to 5.0 nm, there exists a temperature range in which the transition from the body-centered cubic phase to the hexagonal close-packed phase remains incomplete for a long time. In this case, two phases coexist and the initial particle undergoes a strong deformation along the habit plane.     

Mechanism of crystallization of the Ni70Mo10B20 alloy above the glass transition temperature

The phase transformations occurring in the Ni₇₀Mo₁₀B₂₀ alloy in the course of heating above the glass transition temperature are investigated using x-ray diffraction, transmission electron microscopy, high-resolution electron microscopy, and differential scanning calorimetry. It is shown that annealing of the alloy above the glass transition temperature leads to segregation of the amorphous phase into regions enriched with and depleted in molybdenum and/or boron. An increase in the temperature or time of annealing is accompanied by primary crystallization in regions of each type. Crystallization of the regions enriched with molybdenum results in the formation of face-centered cubic crystals of a molybdenum solid solution in nickel (phase 2). Nickel boride crystallizes in the regions enriched with boron. The face-centered cubic phase (phase 1), which is similar to pure nickel, crystallizes in the regions depleted in molybdenum and boron. Nanocrystals of phase 1 are free of defects. Nanocrystals of phase 2 with larger sizes contain a great number of defects.     

Laser modification of silver nanoclusters in SiO2 thin films

Thin films of silica containing silver nanoclusters have been deposited by magnetron co-sputtering followed by thermal annealing. Laser modification of the mean cluster size was performed using the fourth harmonic of a Nd:YAG laser with energies of between 35 and 125 mJ/cm². The mean size of the clusters was estimated from the shape of the plasmon resonance band in the optical absorption spectra with the help of a computer simulation based on the Mie theory in static approximation. It was found that laser treatment with fluences above a certain threshold leads to a reduction of the mean size of the clusters and this reduction is greater for greater fluences. After a long treatment with the same fluence the effect saturates. The final mean size of the clusters after saturation depends only on the laser fluence and not on the initial mean cluster size. When lower laser fluences were used it was possible after laser annealing to return the mean cluster size to its initial value by thermal annealing. In this way by using a combination of laser treatment and thermal annealing a predetermined mean cluster size could be achieved. The mechanism of laser-induced cluster-size modification is discussed. PACS 81.07.-b; 42.62.-b; 36.40.Qv     

Computer simulation of crystal structure formation upon transition from amorphous state

The structure of a solid has been studied by the molecular dynamics technique upon transition from the amorphous state to the crystalline state. The influence of initial conditions in the simulation of an amorphous sample and the temperature of its heating on the resulting structure is examined. It is found that structures of two types can be formed in the sample: single crystals consisting of face-centered cubic (fcc) and hexagonal close-packed (hcp) cells with a small number of pentahedral cells in the boundary region of the sample and block crystals with an ordered pentahedral structure composed of fcc, hcp, pentahedral, and icosahedral cells. Linear chains of vacancies are revealed at the boundaries of blocks.     

Crystal structure of low-temperature rubidium monoaluminate modification

Rubidium monoaluminate RbAlO₂ has been studied by powder neutron diffraction and differential scanning calorimetry. A structural phase transition has been found at 1050°C. It is shown that the low-temperature modification RbAlO2 has the orthorhombic structure (Pnma, a = 0.5570(2) nm, b = 1.1189(4) nm, c = 1.5818(6) nm) close to the crystal structures of low-temperature modifications RbGaO₂ and RbFeO₂, not a face-centered cubic structure, as assumed previously.     

Ordering in binary FCC alloys

A new method of approximation for studying the order-disorder transition in binary alloys is presented. The formulation is in terms of face-centered cubic alloys, although the method can also be applied to other structures. The technique is essentially a generalization of the constant-coupling approximation. We have applied the principles of that method to derive the free energy of the alloy using a tetrahedral cluster of nearest neighbouring sites as the basic unit of the calculation. We only consider the case of nearest neighbour pair interactions, but show how the method can be generalized to include many body and second neighbour interactions. Numerical results are presented and comparison of these results is made with results of cluster variation calculations on the same system and with experimental results on the copper-gold alloy system.     

Ordering in model metallic glass upon external homogeneous shear

Nonequilibrium molecular dynamics simulations are performed for model metallic glass upon external homogeneous shear. The results from cluster analysis reveal the positive influence of external shear on the structural ordering in the considered glassy system. It is found that homogeneous shear facilitates the appearance of crystalline clusters whose structure is characterized by face-centered cubic and hexagonal symmetries.     

Molecular dynamics investigation of the structural stability of body-centered cubic zirconium nanofilms

The influence of the film thickness and temperature on the phase stability of body-centered cubic (BCC) zirconium in infinite films with different crystallographic orientations has been investigated using the molecular dynamics method with a many-body interatomic interaction potential obtained within the embedded atom model. The calculations have been performed for BCC zirconium films with thicknesses ranging from 2 to 13 nm and with low Miller indices (001), (110), and (111). It has been shown that the BCC(001) zirconium nanofilms with thicknesses up to 6.1 nm, which are formed in the temperature range from 500 to 1300 K, undergo a reorientational phase transition through an intermediate metastable face-centered cubic (FCC) phase with the subsequent transformation into the hexagonal close-packed (HCP) structure (BCC(001)-FCC-BCC??(110)-HCP). When the temperature of initialization of the films is 500 K and below, the BCC-FCC transformation is observed and the FCC phase remains stable. The (110) films are characterized by a strong dependence of the temperature of the BCC-HCP phase transition on the film thickness up to values of 5.8 nm. In the (111) films, the amorphization of the initial BCC phase with the subsequent formation of the BCC phase with a twin structure is observed.     

Multiphase density functional theory parameterization of the interatomic potential for silver and gold

The ground state energies of Ag and Au in the face-centered cubic (FCC), body-centeredcubic (BCC), simple cubic (SC) and the hypothetical diamond-like phase, and dimer werecalculated as a function of bond length using density functional theory (DFT). Theseenergies were then used to parameterize the many-body Gupta potential for Ag and Au. Wepropose a new parameterization scheme that adopts coordination dependence of theparameters using the well-known Tersoff potential as its starting point. Thisparameterization, over several phases of Ag and Au, was performed to guaranteetransferability of the potentials and to make them appropriate for studies of relatednanostructures. Depending on the structure, the energetics of the surface atoms play acrucial role in determining the details of the nanostructure. The accuracy of theparameters was tested by performing a 2?ns MD simulation of a cluster of 55 Ag?atoms – awell studied cluster of Ag, the most stable structure being the icosahedral one. Withinthis time scale, the initial FCC lattice was found to transform to the icosahedralstructure at room temperature. The new set of parameters for Ag was then used in atemperature dependent atom-by-atom deposition of Ag nanoclusters of up to 1000 atoms. Wefind a deposition temperature of 500?±?50?K where low energy clusters are generated,suggesting an optimal annealing temperature of 500?K for Ag cluster synthesis. Surfaceenergies were also calculated via a 3 ns MD simulation.