Ab initio study of H and He migrations in β-phase Sc, Y, and Er hydrides

Ab initio calculations based on the density functional theory have been performed to investigate the migrations of hydrogen(H) and helium(He) atoms in β-phase scandium(Sc),yttrium(Y),and erbium(Er) hydrides with three different ratios of H to metal.The results show that the migration mechanisms of H and He atoms mainly depend on the crystal structures of hydrides,but their energy barriers are affected by the host-lattice in metal hydrides.The formation energies of octahedral-occupancy H(H oct) and tetrahedral vacancy(V tet) pairs are almost the same(about 1.2 eV).It is of interest to note that the migration barriers of H increase with increasing host-lattice atomic number.In addition,the results show that the favorable migration mechanism of He depends slightly on the V tet in the Sc hydride,but strongly on that in the Y and Er hydrides,which may account for different behaviours of initial He release from ScT2 and ErT2.     

Thermodynamics and defect structures of silver sulfide

Published measurements of sulfur vapor pressure and silver electromotive force were used to determine thermodynamic properties of silver sulfide above 379 K. They were Gibbs-Duhem integrated to estimate the formation properties of stoichiometric Ag₂S of fcc, bcc, and monoclinic crystal structures. Statistical thermodynamics was applied to estimate free energies and find possible atom arrangements in off-stoichiometric silver sulfide. Theoretical calculations show that silver vacancies and atoms may be in quasi-chemical equilibrium between tetrahedral and octahedral sites in the fcc structure and between two states of atoms within tetrahedral sites in the bcc structure and within octahedral sites in the monoclinic structure. A strong indication is that vacancy clusters should predominate, each containing four-atom vacancies in the fcc phase and three-atom vacancies in the bcc phase.     

Trapping of helium atom by vacancy in tungsten: a density functional theory study

The interaction between helium (He) atom and vacancy defect in tungsten (W) has been investigated by using first-principles simulations. We have obtained that the most stable site for He in tungsten is the substitutional position because He can keep its own electronic structure at this position. In the studied tungsten system, vacancy can act as a trapping center for surrounding He atom with negative trapping energy. The migration behaviors of He atom at tetrahedral interstitial site in W, which can be trapped by vacancy but the final position is almost unchanged comparing with its initial position through structural relaxation, have been predicted and discussed. It is also found that single He atom prefers to go through an octahedral site rather than through a direct path to the vacancy, and the stronger the interaction between He atom and vacancy is, the lower the migration barrier will be.     

嵌入原子法计算金属钚中点缺陷的能量

钚因放射性衰变而出现老化效应.钚中点缺陷的性质和行为是理解钚老化效应的一个基础和前提.运用分子动力学模拟技术,计算了金属钚中点缺陷和点缺陷团簇的形成能和结合能.其中钚-钚、钚-氦和氦-氦相互作用势分别采用嵌入原子多体势、Morse对势和Lennard-Jones对势.计算结果表明,单个自间隙原子易以〈100〉哑铃状形态存在;间隙氦原子在理想晶格的八面体间隙位置相对较为稳定;氦原子与空位的结合能较大,在钚的自辐照过程中两者易于结合并形成氦-空位团簇;氦-空位团簇的形成能随氦原子数的增加而增大,当氦与空位的数     

First-principles study of the crystal structures and electronic properties of LaNi5TxHey tritide

The micro-arrangement of helium atoms and electronic properties of tritides LaNi₅T_xHe_y (x=5, 5.5, 6, 6.5; y=0.5, 1.0) have been systematically investigated by means of the full-potential linearized augmented plane wave (FLAPW) method with the generalized gradient approximation (GGA). Those optimized results indicate that helium atoms prefer to occupy the tetrahedral interstitial sites (6c₁) in LaNi₅ tritides. From the analysis of the electronic structure, a strong and narrow peak appears in the low energy region (about −4.0 eV), which is due to the contribution of the He-s band. With increasing in the helium content, the empty band in the low energy region gradually moves to the right. Compared with H atoms, the interactions between He atom and La, Ni atoms are quite weaker, which can easily cause the pulverization of the host alloy.     

High-resolution mass spectrometric study of pure helium droplets,and droplets doped with krypton

Mass spectra of doped and undoped helium droplets are presented. The high resolution of the time-of-flight spectrometer (m/Δm ≅ 5000) makes it possible to fully resolve small helium cluster ions from impurities and to unambiguously identify abundance anomalies in the size distribution of He _n ⁺. The yield of He₄ ⁺ shows the well-known enhancement relative to other small cluster ions when the expansion changes from sub- to supercritical, provided the electron energy exceeds a value of 40 ± 1 eV, the threshold for formation of electronically excited ions. Upon doping with krypton, pure Kr _n ⁺ cluster ions containing up to 41 Kr atoms are observed. The spectra exhibit abundance anomalies at 13, 16, 19, 22 & 23, 26 and 29, in agreement with spectra obtained by ionization of bare krypton clusters that are formed in neat supersonic beams. Mixed clusters He _m Kr⁺ indicate closure of a solvation shell at m = 12.     

First-principles study of helium clustering at initial stage in ThO_2

The clustering behavior of helium atoms in thorium dioxide has been investigated by first-principles calculations. The results show that He atoms tend to form a cluster around an octahedral interstitial site(OIS). As the concentration of He atoms in ThO_2 increases, the strain induced by the He atoms increases and the octahedral interstitial site is not large enough to accommodate a large cluster, such as a He hexamer. We considered three different Schottky defect(SD) configurations(SD_1, SD_2, and SD_3). When He atoms are located in the SD sites, the strain induced by the He atoms is released and the incorporation and binding energies decrease. The He trimer is the most stable cluster in SD_1. Large He clusters, such as a He hexamer, are also stable in the SDs.     

Specific features of the excitation spectrum of helium II in a plasma initiated by an electron beam

The emission of a low-pressure helium plasma (P≤2 Torr) initiated by a monochromatic electron beam is investigated. It is found that an increase in the current leads to a drastic increase in the rate of charge exchange of doubly charged helium ions. The assumption is made that inelastic collisions of He⁺⁺ ions with metastable helium atoms provide the main channel of charge exchange of these ions due to the reaction He⁺⁺+Hem→ He⁺*+He ₀ ⁺ .     

Hydrogen storage capabilities of the most stable isomers of NanBm (m+n=6) clusters

The most stable isomers of NanBm(m+n=6) clusters and their hydrogen storage properties are investigated by means of density functional theory with a 6-311+G(d) basis set. To study the hydrogen storage properties,all of the stable structures of Na n BmHx (m+n=6) clusters have been optimized. It shows that boron atoms of Na n B m are separated from the other boron atoms,and form satellite BHx (x=3,4) clusters around the centre,which attach to the system by a bridging bond of a hydrogen atom or an Na atom. Compared with the hydrogen storage capabilities,the Na3B3 has the highest hydrogen storage capacity among Na n B m clusters. The binding energies,interaction energies of hydrogen atom with Na n B m clusters and second difference in energy of Na3B3Hx clusters have been calculated. The results show that the stability of the Na n B m H x clusters present an odd-even oscillatory effect,as the number of H atoms increases.     

Trap mutation in He-doped ion-implanted tungsten

In this work, we report on an investigation of the defect complexes InVe₂He _n in tungsten by means of PAC. The release steps InVe₂He _n InV₂He _n-1 + He were identified forn=1t–5. The dissociation energies, in the range of 2.9–4.5 eV, agree perfectly with the values that have been previously determined by means of THDS. The quadrupole frequency is about 122 Mrad/s forn=1,2 and about 101 Mrad/s forn=3,4. These values are smaller than the frequency of the undecorated vacancy (n=0). The vacancy mutates into a divacancy if it is filled with about 10 He atoms, giving rise to a quadrupole frequency of about 218 Mrad/s. This so-called trap mutation ultimately leads to bubble information. We observed at least three different bubble-associated quadrupole interactions.     

Density functional theory study of AunMn(n=1-8) clusters

Equilibrium geometries, relative stabilities, and magnetic properties of small Au_nMn (n=1-8) clusters have been investigated using density functional theory at the PW91P86 level. It is found that Mn atoms in the ground state Au_nMn isomers tend to occupy the most highly coordinated position and the lowest energy structure of Au_nMn clusters with even n is similar to that of pure Au_n+1 clusters, except for n=2. The substitution of Au atom in Au_n+1 cluster by a Mn atom improves the stability of the host clusters. Maximum peaks are observed for Au_nMn clusters at n=2, 4 on the size dependence of second-order energy differences and fragmentation energies, implying that the two clusters possess relatively higher stability. The HOMO-LUMO energy gaps of the ground state Au_nMn clusters show a pronounced odd-even oscillation with the number of Au atoms, and the energy gap of Au₂Mn cluster is the biggest among all the clusters. The magnetism calculations indicate that the total magnetic moment of Au_nMn cluster, which has a very large magnetic moment in comparison to the pure Au_n+1 cluster, is mainly localized on Mn atom.     

Ab initio study of the formation of vacancy and hydrogen-vacancy complexes in palladium and its hydride

We report on the results of ab initio calculations of vacancy and hydrogen-vacancy complexes in palladium and palladium hydride. Comparative analysis of the energies of the formation of defect complexes in palladium and its hydride has revealed that the formation of vacancy clusters is easier in the palladium hydride structure. Investigation of hydrogen-vacancy complexes in bulk crystalline palladium has shown that a hydrogen atom and a vacancy interact to form a stable hydrogen-vacancy (H-Vac) defect complex with a binding energy of E _b = ?0.21 eV. To investigate the initial stage in the formation of hydrogen-vacancy complexes (H _n -Vac _m ), we consider the clusterization of defects into clusters containing H-Vac and H₂-Vac complexes as a structural unit. It is found that hydrogen-vacancy complexes form 2D defect structures in palladium in the (100)-type planes.     

Ab initio pseudopotential study of vacancies and self-interstitials in hcp titanium

By means of an ab initio plane-wave pseudopotential method, monovacancy, divacancy and self-interstitials in hcp titanium are investigated. The calculated monovacancy formation energy is 1.97 eV, which is in excellent agreement with other theoretical calculations, and agrees qualitatively with published experimental results. The relaxation of the atoms around a single vacancy is observed to be small. Two divacancy configurations, the in-plane and the off-plane, have also been shown to be equally stable. With regards to the interstitials, of the eight configurations studied, two (octahedral and basal octahedral) have relatively lower formation energies and are, thus, the most likely stable configurations. We find small energy differences between them, suggesting their possible co-existence. It is also observed that the tetrahedral configuration decays to a split dumbbell configuration, whereas both the basal tetrahedral and the basal pseudocrowdion interstitials decay to the basal octahedral configuration. Using the nudged elastic band method (NEB), we determine a possible minimum energy path (MEP) for the diffusion of self-interstitial titanium atoms from an octahedral site to the nearest octahedral site. The energy barrier for this migration mechanism is shown to be about 0.20 eV.     

Localized diffusion of helium atoms around indium impurities in aluminium observed by means of perturbed angular correlations

The behaviour of He atoms implanted in ¹¹¹In doped Al has been investigated by means of perturbed angular correlation (PAC) measurements. The onset of He mobility was found to be at about 250K, probably due to vacancy-assisted migration. Mobile helium is effectively trapped at In impurities in small vacancy clusters that accomodate at most 11 He atoms. The PAC spectra taken at temperatures from about 510 K to 670 K exhibit a relaxation effect that is ascribed to hopping of He atoms from one vacancy to another, the saddle-point energy for this localized diffusion being 0.67(5) eV. A tentative model of the cluster is given.     

Effect of helium/argon gas ratio in a He-Ar-Cu<Superscript>+</Superscript> IR hollow-cathode discharge laser: modeling study and comparison with experiments

The He-Ar-Cu⁺ IR laser operates in a hollow-cathode discharge, typically in a mixture of helium with a few-% Ar. The population inversion of the Cu⁺ ion levels, responsible for laser action, is attributed to asymmetric charge transfer between He⁺ ions and sputtered Cu atoms. The Ar gas is added to promote sputtering of the Cu cathode. In this paper, a hybrid modeling network consisting of several different models for the various plasma species present in a He-Ar-Cu hollow-cathode discharge is applied to investigate the effect of Ar concentration in the gas mixture on the discharge behavior, and to find the optimum He/Ar gas ratio for laser operation. It is found that the densities of electrons, Ar⁺ ions, Ar_m ^* metastable atoms, sputtered Cu atoms and Cu⁺ ions increase upon the addition of more Ar gas, whereas the densities of He⁺ ions, He₂ ⁺ ions and He_m ^* metastable atoms drop considerably. The product of the calculated Cu atom and He⁺ ion densities, which determines the production rate of the upper laser levels, and hence probably also the laser output power, is found to reach a maximum around 1–5 % Ar addition. This calculation result is compared to experimental measurements, and reasonable agreement has been reached. Received: 14 October 2002 / Revised version: 28 November 2002 / Published online: 19 March 2003 RID="*" ID="*"Corresponding author. Fax: +32-3/820-23-76, E-mail: annemie.bogaerts@ua.ac.be     

Study of clusters of interest for liquid ionic alloys

Calculations are reported of the total energies and related quantities of sequences of small clusters of the form A_m Pb_n, where A is an alkali atom, n <6 and m < 9. The object of this study is to shed light on the stoichiometry and the possible formation of complexes in A-Pb liquid alloys. The calculations are performed using empty core pseudopotentials and the spherical average approximation for the cluster. The results are insensitive to the choice of alkali atom apart from a smooth trend with the progression from Li to Cs. The calculated total energies suggest that clusters with compositions A₄Pb and A₄Pb₄ are very stable against a change in the number of Pb or A atoms and support the possibility of these clusters forming in the liquid alloys. This stability arises from an electronic shell-closing effect.     

He原子掺杂铝材料的第一性原理研究

采用基于第一性原理的平面波超软赝势方法,结合广义梯度近似(GGA),计算了铝及铝晶胞间隙位置掺入He原子后体系的几何结构、电子结构、总体能量和电荷布居值.计算结果表明:随着氦在金属铝中逐渐形成,铝晶胞体系会发生晶格畸变,但总的趋势是He在铝体系的八面体位置的晶格畸变小于其在四面体位置的晶格畸变.He在铝晶胞八面体和四面体间隙的杂质形成能分别为1.3367 eV和2.4411 eV.由此可知,He在铝晶胞中最稳定位置是八面体间隙位置.同时,文中还从原子尺度层面分析了He原子在铝晶胞中的占位及其键合性质,讨论 关键词： 铝材料 第一性原理 形成能     

Density functional study of small cobalt-platinum nanoalloy clusters

The structural, energetic, electronic and magnetic properties of small bimetallic Co_nPt_m (n+m≤5) nanoalloy clusters are investigated by density functional theory within the generalized gradient approximation. A plausible candidate for the ground state isomer and the other possible local minima, binding energies, relative stabilities, magnetic moments, the highest occupied and the lowest unoccupied molecular orbital energy gaps have been calculated. It is found as a general trend that average binding energies of Co-Pt bimetallic clusters increase with Pt doping. Planar structures of pure Co clusters become 3D with the addition of Pt atoms. CoPt₂, Co₂Pt₂, Co₃Pt₂, and CoPt₄ nanoalloys are identified as the most stable species since they have higher second finite difference in energy than the others. Pt doping decreases the total spin magnetic moment gradually. A rule for the prediction of the total spin moments of small Co-Pt bimetallic clusters is derived.