Interfacial contribution to cluster free energy

The Monte Carlo technique of “overlapping distributions” is used for computing directly the free energy difference F_{N + 1} ?F_N between two clusters containing respectively N + 1 and N solute atoms, in the square and the simple cubic Ising model with nearest neighbour interactions. High accuracy results are obtained within reasonable computer times. The capillarity approximation gives a good fit to the data, provided the following is taken into account: (i) the specific bulk and surface energies are given their macroscopic equilibrium values; (ii) a curvature correction to the surface specific energy has to be introduced: it is positive for two dimensions and negative for three dimensions; (iii) a size independent term is to be added in three dimensions; it may be viewed as a corner contribution; (iv) the coefficient of the logarithmic term is given its more recent value. When introduced in the master equation which describes the kinetics of the cluster population, within the simplifying assumptions of the classical nucleation theory, good agreement is found, for the shapes of the cluster size distributions, with the numerical experiments on the kinetic Ising model in two dimensions. However, the time scales of both computations do not match linearly. Possible reasons for this discrepancy are discussed.     

Relativistic double differential cross sections for Compton scattering by bound electrons: Test at low photon energies and predictions at intermediate photon energies

Cross section profiles d²σ/dΩdω′ for Compton scattering of photons by bound electrons are calculated for all subshells of the atom. Results obtained from the form factor approximation and from a relativistic version of the impulse approximation are compared with experimental data for Cu and Pb at a scattering angle ofθ=145° and a photon energy of 662 keV. The impulse approximation proves to be superior to the form factor approximation and is used to predict cross section profiles for a primary energy of 50 MeV and different scattering angles and charge numbers. It is shown that only for the heaviest atoms and scattering angles belowθ=5° there is a non-negligible contribution of Compton scattering to the elastic peak.     

The theoretical and experimental study of the ionization processes during the low energy ion sputtering

The process by which atoms are ionized as they are sputtered from a metal surface has been analyzed both theoretically and experimentally. In the theoretical part the expressions for ionization coefficient R⁺ of atoms having the ionization energy much larger than the metal work function have been derived using a molecular orbital method. The effect of the level crossing was estimated in an approximate way. In the experimental part the SIMS experiments on clean Ni and Al surfaces and on Ni surface covered with a submonolayer of adsorbed K, Na and Al are reported. It has been found and it is for the first time reported that the energy distribution of ions sputtered from a submonolayer of adatoms is independent of energy (200–2500 eV) and mass (Ar⁺ Xe⁺ of incident ions and depends only upon the adsorption energy of the adatom. The energy distribution of ions sputtered from bulk samples has been found dependent on the primary ion energy. The measurement of the absolute value of R⁺ has shown that there is a strong correlation between the number of the adatom valence d-electrons and the value of R⁺, the value of R⁺ being smaller for atoms with more d-electrons. These experimental data have been compared with the theoretical expressions and the important role of the mechanism which takes into account the bending of the adatom energy level has been assessed.     

Surface energy and pressure of diamond and silicon nanocrystals

Based on the pair potential of interatomic interaction, we study the dependence of various properties of diamond and silicon nanocrystals with a free surface on size, surface shape, and temperature. A model nanocrystal has the form of a parallelepiped faceted by {100} planes with a square base. The number of atoms N in the nanocrystals is varied from 5 to infinity. The Debye temperature, Gruneisen parameter, specific surface energy, isochoric derivative of specific surface energy with respect to temperature, and surface pressure are calculated as a function of the size and shape of diamond and silicon nanocrystals at temperatures ranging from 20 K to the melting point. The surface pressure P _sf(N) ∼ N ^−1/3 is much lower than the pressure calculated by the Laplace formula for similar nanocrystals for given values of density, temperature, and number of atoms. As the temperature increases from 20 K to the melting point, the isotherm P _sf(N) lowers and changes the shape of the dependence on N; at high temperatures, it goes to the region of extension of small nanocrystals of diamond and silicon.     

Dependence of the surface energy on the size and shape of a nanocrystal

An expression is derived for the surface energy σ as a function of the size and shape of a nanocrystal. It is shown that the wider the deviation of the shape parameter f from unity, the more pronounced the decrease in the surface energy σ with a decrease in the number N of atoms in the nanocrystal. The dependences of the average coordination number, the surface energy, and the melting temperature on the number N exhibit an oscillatory behavior with maxima at points corresponding to numbers of atoms forming a defect-free cube. The surface energy decreases with an increase in the temperature T. It is found that the smaller the nanocrystal size or the greater the deviation of the nanocrystal shape from the thermodynamically most stable shape (a cube), the larger the quantity-(dσ/dT). It is established that the nanocrystal undergoes melting when the surface energy decreases to a value at which it becomes independent of the nanocrystal size and shape. The conditions providing fragmentation and dendritization of the crystal are discussed. It is demonstrated that, at N>1000, the dependence σ(N) coincides, to a high accuracy, with the dependence of the surface tension of the nanocrystal on N. The inference is made that bimorphism is characteristic of nanocrystals. This implies that nanocrystals can have platelike and rodlike shapes with equal probability.     

Effectiveness of the third body in the direct recombination of ions

The dynamics of the three-body recombination of the Cs⁺ and Br^? ions with the formation of products with the lowest internal energy in the presence of the neutral atoms R = Hg, Xe, and Kr as third bodies is studied. The efficiency of the process is characterized by the effectivity function, which represents the dependence of the internal energy of the nascent molecule on the ion encounter energy and the third body energy. The Hg and Xe atoms are demonstrated to exhibit similar efficiencies in stabilizing the CsBr molecules, significantly superior to that of the Kr atom. The effectivity of each third body as an acceptor of excess energy of the molecules formed in recombination is determined by the structure of the potential energy surface of the individual R-Cs⁺-Br^? system, the masses of the third bodies, and the dynamics of three-body collisions leading to recombination.     

The measurement of energy parameters for atoms sputtered in excited states

Ti I lines from excited Ti atoms sputtered from Ti and a variety of Ti compounds by 55 keV Ar⁺ bombardment have been studied and the intensity decay, as a function of distance, has been measured in front of the target surface for normal incidence bombardment. These decay curves have been analyzed using the model of Dzioba et al. The model has been examined with respect to its internal consistency in the predictions for integral and differential yield measurements using several Ti I and an Al I line. Although care must be taken in defining an adequate slit size for each particular decay curve, the integral and differential measurements infer consistent E1 values. These values have been generally found to increase with the excitation energy of the Ti I level studied, and to decrease with surface (or bulk) contamination of O, N, C and B. Selected characteristics of photon emission are discussed in relation to the E1 values obtained.     

Adsorption of sodium and its effect upon some electric properties of clean germanium (111) surfaces

The effect of adsorbed Na on the surface conductivity, Δσ, and surface recombination velocity, S, of a clean (114)Ge surface is studied. The surface conductivity is a complicated function of the surface Na concentration, N_Na; at N_Na ≈ 1.5 × 10¹³ atoms/cm², it has a minimum; at ca. (3–5) × 10¹⁴atoms/cm², it has a maximum. For a monolayer coverage (ca. 7.2 × 10¹⁴atoms/cm²) the values of Δσ are not much different from those of a clean Ge surface. The surface recombination velocity is a three-valued function of the surface potential, U_S (calculated from the Δσ values), depending on the Na overlayer coverage and heat treatment of the sample. Three different surface structures (LEED data) were found to correspond to the three S versus U_S curves reported here. Thermal desorption studies show that Na is desorbed in a wide temperature interval. Two peaks have been isolated, studied and discussed. At low coverages a single peak is found to exist, which obeys the first-order desorption kinetics, with a desorption energy of (52 ± 3)kcal/mol. This peak is attributed to the surface defects. For coverages close to$\text{1}\text{4}$ monolayer a new peak was observed in the spectrum. The desorption energy of this binding state exceeds that of all the other states. When the overlayer coverage is increased, this peak is shifted to higher temperatures, as predicted for a half-order desorption kinetics. By comparing also with LEED data, it may be concluded that this most tightly bound sodium has formed on the Ge(111) surface patches of an ordered structure in which one Na atom is bonded to three Ge atoms.     

Elastic scattering of metastable He(21,3 S) atoms by Na(32 S) atoms at 68 meV

The spectroscopy of metastable states is used to make the first experimental measurement of the total differential elastic-scattering cross sections of metastable helium atoms in 2³ S and 2¹ S states by sodium atoms in the ground state at interaction energy 68 meV in the center-of-mass system. To analyze the experimental data, the partial scattering phases are calculated using the method of phase functions in the optical potential approximation. The analysis makes it possible to give a more detailed interpretation of the structure of the differential cross section. The computed integral cross sections, specifically, Penning ionization, diffusion, viscosity, and spin exchange are discussed.     

Electronic and magnetothermal properties of ferromagnetic clusters

The electronic structures and the magnetothermal properties of nickel clusters have been investigated. Their effective magnetic moments and specific heat capacities have been calculated assuming that the clusters undergo superparamagnetic relaxation. The average magnetic moments are computed adopting Friedel's model of ferromagnetic clusters. The surface effect and the cluster size effect on the thermodynamic properties of these clusters have been analysed based on the mean field theory approximation. The specific heat capacity of Ni clusters for N=300, where N is the number of atoms in the cluster, shows the peak value at T=550 K and exhibits a steady increase with N. The effective potentials and energy eigen values of the clusters as a function of the number of atoms and radius of the cluster have also been calculated self-consistently using the local density approximation (LDA) of the density functional theory (DFT); this has been performed within the framework of the spherical jellium background model (SJBM). The results of this study have been compared with the Stern-Gerlach experimental data and other theoretical results already reported in literature     

Electron energy loss spectroscopy of ethylene on Ag(110) precovered with oxygen: energy dependence of the cross section

The intensities of the CH out-of-plane bending (v₇) and CH stretch (v₁) vibrations of ethylene adsorbed on Ag(l 10) precovered with oxygen have been measured in EELS as a function of beam energy from 2 to 20 eV. The energy dependence of the v₇ vibration is satisfactorily described by the dipole approximation. For the v₁ vibration, which is purely dipole forbidden, an entirely different energy dependence is found, with a maximum intensity at a beam energy of 2 eV. Comparison of the EEL intensities observed experimentally with those predicted from the dipole moments of the free molecule confirms the conclusion that the molecular plane of chemisorbed ethylene is parallel to the surface.     

An investigation of the internal temperature dependence of Pd-Pt cluster beam deposition: A molecular dynamics study

We investigated the internal temperature dependence of the Pd_1−aPt_a cluster beam deposition in the present study via the molecular dynamics simulations of soft-landing. By analysis of the velocity distribution and diffusion coefficient of the bimetallic cluster, Pd atoms with better mobility improved the diffusibility of Pt atoms. The radial composition distribution showed that a Pt-core/Pd-shell structure of the cluster formed at high internal temperatures through migrations of the Pd atoms from inner to surface shells. In the soft-landing process, the diffusing and epitaxial behaviors of the deposited clusters mainly depended on the internal temperature because the incident energy of the cluster was very small. By depositing clusters at high internal temperatures, we obtained a thin film of good epitaxial growth as the energetic cluster impact. Furthermore, nonepitaxial configurations such as scattered nonepitaxial atoms, misoriented particles, and grain boundaries of (1 1 1) planes were produced in the growth of the cluster-assembled film. As the size of the incident cluster increased, the internal temperature of the cluster needed for better interfacial diffusion and contact epitaxy on the substrate also rose.     

State selective detection of sputtered Al neutrals by resonant laser ionization SNMS

It is important to optimize the resonance ionization efficiency of the sputtered particle by evaluating the internal energy of it. And also the dependence of the change of the internal energy of it on primary ion species and accelerating voltages was investigated. For this study, we developed proto-type resonance laser ionization SNMS instrument, which is a quadrupole SIMS apparatus combined with a wavelength tunable laser. The internal energy of the sputtered aluminum atoms, which has lowly lying excited state (112 cm⁻¹) on the ground state, was monitored. As the results, the internal energy of the sputtered aluminum atoms was not influenced by the change of the surface work function and primary ion beam energy at all. On the contrary, the density on lowly lying excited state drastically increased due to the existence of the oxygen on aluminum surface.     

A scaling theory of clusters in the lattice gas

It is proposed that the number ofp-particle,k-bond lattice gas cluster configurations is of the form exp{σpf(k/p)} in the limitp→t8. A simple modification permits application to finite clusters, with the consequence that asymptotically the cluster partition function is of the droplet form, i.e., Z _p =exp[kp{itμp^1?1/d }+O(ln p)]. The scaling function for two-dimensional lattices is determined numerically and is found to be qualitatively universal. The scaling theory is used to investigate the size dependence of the surface free energy. The surface tension of small clusters can significantly exceed its limiting value. For intermediate cluster sizes (～100 particles) there is a modest reduction in surface tension, in accord with Tolman's prediction and the results of recent Monte Carlo studies.     

Secondary ion emission by nonadiabatic dissociation of nascent ion molecules with energies depending on solid composition

A new model of the emission of positive secondary ions Me⁺ from metal oxides is proposed to reproduce the strong mass dependence of their yield. The mass dependent aspects of this model are discussed and mathematically formulated. The energy transport in the collision cascades depends strongly on the mass ratio of the atoms involved. An approximation of the energy distribution of surface atoms is made which includes this mass effect. Surface molecule collisions lead to the emission of ions. They again depend on the mass ratio of the molecule's constituents. It is made plausible that particle complexes leave the surface only neutrally. In a nonadiabatic dissociation process free ions can be created outside the surface potential barrier. There is only a very low probability for neutralization depending on the mass of the ions involved. The model calculation reported in Part II of this paper reproduces the strong mass dependence experimentally observed. In Part I the new emission conception is additionally confirmed by the qualitative explanation of other Me⁺ emission effects: difference in the energy distribution of Me⁰ and Me⁺, change of the energy distribution of Me⁺ ions during oxygen exposure experiments, difference in the Me⁺ emission of metals with high (Ti) and low (Co) affinity to oxygen during oxygen exposure experiments.     

On the surface properties of a nanodiamond

The dependences of the specific surface energy, the surface tension, and the surface pressure on the size, the surface shape, and the temperature of a nanodiamond with a free surface have been investigated using the Mie-Lennard-Jones interatomic interaction potential. The nanocrystal has the form of a parallelepiped faceted by the (100) planes with a square base. The number of atoms N in the nanocrystal varies from 5 to ∞. The isothermal isomorphic dependences of the specific surface energy, its isochoric derivative with respect to the temperature, the surface tension, and the surface pressure on the nanodiamond size have been calculated at temperatures ranging from 20 to 4300 K. According to the results of the calculations, the surface energy under this conditions is positive, which indicates that the nanodiamond cannot be fragmented at temperatures up to 4300 K. The surface pressure for the nanodiamond P _sf (N) ∼ N ^−1/3 is considerably less than the Laplace pressure P _ls (N)^−1/3 ∼ N ^−1/3 for the same nanocrystal at the given values of the temperature, the density, and the number of atoms N. As the temperature increases from 20 to 4300 K, the lowering of the isotherm P _sf (N) is considerably more pronounced than that of the isotherm P _ls (N). At high temperatures, the isotherm P _sf (N) changes the shape of the size dependence and goes to the range of extension of small nanocrystals. It has been demonstrated that the lattice parameter of the nanodiamond can either decrease or increase with a decrease in the nanocrystal size. The most significant change in the lattice parameter of the nanodiamond is observed at temperatures below 1000 K.     

Photoluminescence quantum and surface states of excitons in ZnSe and CdS nanoclusters

The optical spectra of quantum dots (QDs) of CdS and ZnSe grown in borosilicate glass by the sol-gel method are obtained and analyzed. It is found that at concentrations of the two semiconductors x<0.06% the emission spectra are due to annihilation of free (internal) excitons in quantum states. The mean size of the quantum dots for a given concentration of ZnSe and CdS is calculated and found to be in good agreement with the X-ray data, and the exciton binding energy is calculated with allowance for the dielectric mismatch between the semiconductor and matrix. It is proposed that this mismatch may be the cause giving rise to the exciton percolation level that is observed in QD arrays for both systems at x>0.06%. The emission from the surface level of CdS QDs in the region ~2.7 eV, formed by the outer atoms with dangling bonds, is observed for the first time, as is the emission band from surface localized states. The relation between the position of the maximum of this band and the energy of the 1S state of the free exciton is established. It is shown that the properties of surface localized states are largely similar to the analogous properties of localized states of 3D (amorphous semiconductors, substitutional solid solutions of substitution) and 2D (quantum wells and superlattices) structures.     

Photoionization cross section of atomic nitrogen calculated by the many-channel quantum defect method

The many-channel quantum defect method has been used for the calculation of the photoionization cross section of ground-state nitrogen atoms in the dipole length approximation. The calculations couple three channels corresponding to the 2s ² 2p ² and 2s2p ³ configurations of the residual ion. The results obtained are in agreement with experiment for the energy region between the ionization limit and 1 rydberg unit beyond.