An association theory for the formation of ion oligomers and its application to 1-1 electrolytes

A theory for modelling electrolyte solutions which includes the formation of ion clusters of different size has been developed in the framework of the primitive model. In primitive models the solvent is described as a dielectric continuum and the solvent–solute interactions are neglected. For the dielectric constant the value of the pure solvent has been used. The ion cluster distribution is calculated from the mass action law. The association constants are related to integrals over the cluster distribution functions which are calculated with the Kirkwood superposition approximation from low density pair distribution functions. The ion clusters are defined by a certain distance which rules if two ions belong to the same cluster. This so-called Bjerrum distance is chosen according to fundamental investigations of the structure of ion cluster. All ion clusters are modelled as hard spheres. For the free ions and charged clusters the mean spherical approximation expression for the Coulomb interaction is added. The co-volumes of the ion clusters have been taken from the investigation of the ion cluster structures, and are consistent with the definition of an ion cluster chosen here.     

Metallic clusters in the AlN ceramic

Characterization of the local environment of metallic ions (Cu, Fe, Ti, Ni and Er) implanted in the ceramic matrix AlN have led us to conclude that the heat of formation (\Delta H) of the implanted ion nitride (I-N) is the parameter which has to be considered in order to predict the final system. When ΔH_I-N is negative, bonds between the implanted ion and nitrogen atoms are formed, when ΔH_I-N is positive, clusters of the implanted ion are formed. Moreover, we give some physical characteristics of the Cu and Ni clusters in the AlN matrix and show the differences between imbedded and deposited clusters of the same size. This revised version was published online in August 2006 with corrections to the Cover Date.     

氯化钾水溶液微观结构的分子动力学模拟研究

氯化钾水溶液不同于氯化钠的,其在低温下只能形成无水盐和冰.现有研究表明在氯化钠水溶液中不仅存在着水分子连续分布的区域与离子团簇,而且这二者的物质组成也与该溶液所形成晶体的分别对应.为了探寻其他溶液中是否存在此类对应关系,并考察溶液的微观结构,本文采用分子动力学方法对氯化钾水溶液进行了研究,表明了该溶液的一些性质.氯化钾水溶液中K⁺-K⁺和Cl^--Cl^-径向分布函数的特征具有一致性,峰的最大值所对应的位置都分别相同,明显不同于氯化钠水溶液的.系列时刻下瞬态图像内O到其最近离子距离中最大值的统计结果表明氯化钾水溶液中存在着一定大小的水分子连续分布的区域,其平均尺寸至少为2.26 nm;瞬态图像中K⁺与其最近邻Cl^-之间的距离主要分布在0.28 nm～0.38 nm之间,占比约为97.4%;溶液中存在着较大和较小两类离子团簇,较大团簇的平均尺寸为1.73nm,平均离子数是25.0,其内部的离子与周围离子之间具有与氯化钾晶体类似的结构;这些结果表明氯化钾水溶液中也...     

Structures and reactions of hydrated biomolecular cluster ions

Photo-induced reactions and metastable decompositions of cluster ions containing glycine, tryptophan, tryptophanylglicine and [Fe(III)-protoporphyrin]⁺ (hemin⁺) ions solvated with water molecules are studied with electrospray ionization (ESI). The ESI ion source is improved to produce hydrated biomolecular cluster ions. Metastable decompositions of the hydrated clusters following primary mass selection are measured to determine the incremental solvent binding energies for the clusters by using evaporative ensemble model. From these experimental findings, stability of the cluster ions is discussed in terms of delocalization of ionic charges. We also measure the photodissociation yields of mass-selected water clusters containing hemin⁺ ions at 355 and 532 nm. The mass spectra of photofragments show the β-cleavage of carboxymethyl groups in addition to the evaporation of solvent molecules.     

Understanding the influence of nanoenvironment on luminescence of rare-earth ions

This paper presents an overview of the recent results on upconversion and photoluminescence of rare-earth ions in nanoenvironments. The role of the rare-earth ion concentration, crystal size and crystal phase on the up and downconversion emission of rare-earth ions in oxide nanocrystals and their underlying mechanisms are discussed. It is also found that the luminescence lifetime of the excited state rare-earth ions is sensitive to the particle crystalline phase and size. The analysis suggests that the modifications of radiative and nonradiative relaxation mechanisms are due to local symmetry structure of the host lattice and crystal size respectively     

Effect of water–methanol content on the structure of Nafion in the sandwich model and solvent dynamics in nano-channels; a molecular dynamics study

Continuing an ongoing study, molecular dynamics (MD) simulations were performed to investigate the effects of methanol concentration on Nafion morphology, such as the size of solvent cluster, solvent location, and polymer structure via the sandwich model. Our survey shows that high methanol concentrations resulted in increment of solvent cluster size in Nafion membrane. The sulfonic acid clusters also befall much in order as subsequent layers of such ionic clusters are formed. The number of neighbouring hydronium ions around a sulfur atom is independent of methanol concentration, but the first shell of hydronium and water around sulfonic acid clusters is broader. Although methanol would prefer to interact with water molecules rather than sulfonic acid groups, gathering of methanol molecules via hydrophobic self-aggregation is preferred. Methanol is located closer to the hydrophobic part of the polymer than water, while water is located closer to the hydrophilic part of the polymer. It was found that methanol distributes specifically more than water in nano-channels. Investigation of solvent dynamics in nano-channels shows that diffusion coefficients (D) of water, methanol, and hydronium decrease with increasing methanol concentration and they may be ordered as follows: D _Water?>?D _Methanol?>?D _Hydronium (D _Water?≈?1.6–2.0D _Methanol and D _Methanol?≈?2.1–3.0D _Hydronium).     

Experiments on clusters

In this contribution we discuss four different types of experiments that have been conducted at molecular beams of neutral clusters. The size of particularly stable sodium chloride clusters and their corresponding geometrical structure is inferred from intensity anomalies in mass spectra. This information is obtained either for charged or for neutral clusters depending on whether the clusters are ionized by electron impact or by multiphoton absorption. The important role of fragmentation in mass spectrometry of xenon clusters is revealed by multiphoton ionization; dissociative reactions occurring on the time scale of 10⁻⁷ s with respect to the ionizing event can be analyzed. The solvation energy of negatively charged carbon dioxide clusters as a function of cluster size is obtained from electron attachment spectra. A resonance in the ion yield close to zero eV electron energy signifies that all clusters except for the monomer feature a positive electron affinity. An analysis of the kinetic energy of fragment ions, originating from delayed dissociation of triply charged carbon dioxide clusters, reveals that the size distribution of their fission fragments is extremely symmetric.     

Competition between two forms of ordering in finite Coulomb clusters

The lowest-energy state of spherical clusters made up of single-species charged particles in a three-dimensional confining potential is investigated by molecular dynamics simulations for a system size of 5 x 10(3) to 1.2 x 10(5). The energy per particle is compared between shell-structured clusters and spherical finite-bcc lattices with relaxed surfaces. The shell structure in the interior is the lowest-energy configuration for ion numbers lower than about 10(4), while for higher ion numbers, an interior with bcc ordering surrounded by a few shells on the outside has lower energy. The formation of a small bcc lattice (nucleation) in the shell-structured cluster of 2 x 10(4) ions is observed.     

Co+离子注入单晶TiO2铁磁性来源与微结构研究

在室温下,将能量为80 keV, 注量分别为1×1016和1×1017ions/cm2的Co+离子注入到10 mm×10 mm×0.5 mm的单晶TiO₂样品。在氮气保护下, Co+离子注量为1×1017 ions/cm2时样品在温度为900 ℃的条件下退火30 min。 利用超导量子干涉仪 （SQUID）测量样品磁性, 并应用X射线衍射（XRD）和扩展边X射线吸收精细结构谱（EXAFS）研究Co+离子注入后样品的微观结构。 样品磁性测量结果表明:Co+离子注入后的样品具有室温铁磁性, 并且其饱和磁化强度的大小与Co+离子注量及样品是否经退火处理有关。 EXAFS研究表明: Co元素在Co+离子注量为1×1017ions/cm2的样品中主要以团簇形式存在;样品经退火处理后, Co团簇消失, 并发现Co部分替代TiO₂单晶中的Ti。Co+离子注入后, 在样品中形成Co团簇与否受离子注量的影响。 阐述了样品微观结构与铁磁性来源之间的关系。 At room temperature, monocrystalline plates of rutile (TiO₂) were implanted with cobalt ions of an energy of 80 keV to fluences of 1×1016 and 1×1017 ions/cm2 respectively . The 1×1017 ions/cm2 Co implanted samples were annealed in nitrogen at 900 ℃ for 30 min. The magnetic properties of Co implanted samples were measured with a superconducting quantum interference device magnetometer (SQUID) at room temperature. Furthermore, the X ray diffraction (XRD) and Extended X ray Absorption Fine Structure (EXAFS) were applied to investigate the structural and compositional properties of Co implanted samples. The magnetic measurements of samples showed that the size of the saturation magnetization of the Co implanted samples were related to the fluence of ions, and the saturation magnetization of the sample after annealed decreased significantly. The EXAFS measurements showed the presence of cobalt metallic clusters in the sample implanted to ion fluence of 1×1017 ions/cm2. The Co metallic clusters disappeared in the sample after annealed, and resulted in the oxidized Co, which is presumed to substitute into the Ti site. The formation of Co clusters or not was determined by the ion fluence. The relation between ferromagnetic behavior and microscopic structure of the Co implanted samples is discussed.     

Secondary ion mass spectra of alkali halides

Mass spectra of positive and negative secondary ions from various alkali halides have been measured in the Manitoba time-of-flight mass spectrometer. The ions were produced by Cs⁺ and K⁺ bombardment at primary ion energies of 3 to 19 keV for the positive spectra, and 11 to 28 keV for the negative spectra. The ions measured were those emitted within a time interval ～ 20 ns after the primary ion impact. The secondary ion yields are strongly dependent on the sample composition and treatment; prior irradiation may change the yield by an order of magnitude or more. The secondary ion yields also depend strongly on the energy loss of the primary ion, but the ratio of yields of different cluster ions from a given target is almost independent of this parameter. The results appear to be consistent with models in which the clusters are ejected directly from the target, but do not determine whether or not they possess the original surface structure. The results may also be described by a recombination model if the recombination is essentially complete.     

Structure of Ion-Implanted Alloys with Long-Range Order in a Field Ion Microscope

In the present review we describe the series of investigations in which field ion microscopy is used to study the structural and phase changes in alloys with long-range order and in pure metals after ion implantation by different gas ions. It is demonstrated that ion implantation induces defects of different types spread to considerable depths from the irradiated surface that exceed many times the estimated ion mean free path. It is established that disordering and generation of various defects can be observed under irradiation of the ordered alloy surfaces. In PdCuAg alloys being supersaturated solid solutions, the irradiation provokes the intermittent decomposition. The structure of defects induced by ion implantation including disordered regions, dislocations, dislocation configurations, dislocation barriers, vacancy clusters, and segregations of one of the components is analyzed. The structure and sizes of these defects inside single cascades of displacements are determined.     

Structural characterisation of Ni clusters in AlN via X-ray absorption, X-ray diffraction and transmission electron microscopy

Ni ions were implanted in bulk AlN with the goal to form embedded metallic clusters. Combining several characterisation techniques such as X-ray absorption spectroscopy, X-ray diffraction and high resolution transmission electron microscopy, we determined the lattice parameter of the Ni clusters that display a fcc crystalline structure. The average size increases when the ion fluence is increased or after a thermal treatment. Thanks to moiré fringes observed by high resolution transmission electron microscopy and to satellite peaks seen on the diffraction patterns, we concluded that the annealed Ni clusters orientate their (002) planes on the (101) of AlN. Moreover, the satellite positions allowed us to calculate Ni cluster average diameters, that are in agreement with average sizes deduced by X-ray absorption spectroscopy. Received 25 August 1999 and Received in final form 8 February 2000     

Ripening of subsurface amorphous C clusters formed by low energy He ion bombardment of graphite

Surfaces of highly oriented pyrolytic graphite (HOPG) were bombarded with 100 eV and 500 eV He ions at ion doses of a few 10¹⁵ cm² and temperatures ranging from 300 K to 800 K. AFM images were recorded to investigate the topography of the surfaces after ion bombardment. Supplementary electron energy loss (EEL) and thermal desorption (TD) spectra were measured to determine the C sp² fraction of the bombarded surfaces and the amount of trapped He. The temperature at which He ion bombardment was performed had a drastic effect on the surface structure and topography of the targets on the angstrom-scale and micrometer-scale as well. At 300 K, limited defect atom transport revealed an amorphous but relatively flat HOPG surface. Bombardment at 400 K leads to a granular structure of small protrusions in micrometer-scale AFM images, however, without crystalline order on the surface. The protrusions are due to the formation of subsurface clusters of carbon formed by atoms displaced by ion irradiation. Towards higher temperatures during bombardment the clusters agglomerate and cause the surface layers to bend upwards in dome-like shapes. Simultaneously, the microscopic order of the graphite lattice recovers. At 800 K large areas of the top layer retain their order during bombardment, however, a small number of domes indicate that there still exist some subsurface C clusters. The cluster–cluster distance deduced from the dome distribution indicates that the clusters grow through a ripening process. Annealing of graphite at high temperatures subsequent to ion bombardment at low temperatures is much less effective for recovering the surface crystallinity than ion bombardment at high temperature.     

Distributions of ions in a cluster plasma created by a laser pulse

Energy and charge distributions of ions are calculated for a cluster beam irradiated by a high-power ultrashort laser pulse. It is shown that the self-consistent field of a cluster ionized by the laser beam strongly affects the characteristics of the ion distributions obtained after the cluster explodes. The mean concentration of atoms bound into clusters in a beam, the cluster size distribution, and the focal-spot diameter are found to have a weak effect on both energy and charge distributions of the ions, whereas the energy spectrum of the produced ions is determined by the mean cluster size.     

Paul阱中存储离子的研究

根据Paul离子阱结构及电场分布特点,列出阱内离子运动方程并求解,对其中离子运动、硅团簇离子碰撞解离反应进行了分析.     

Ions colliding with cold polycyclic aromatic hydrocarbon clusters

We report the first experimental study of ions interacting with clusters of polycyclic aromatic hydrocarbon (PAH) molecules. Collisions between 11.25 keV 3He+ or 360 keV 129Xe20+ and weakly bound clusters of one of the smallest PAH molecules, anthracene, show that C14H10 clusters have much higher tendencies to fragment in ion collisions than other weakly bound clusters. The ionization is dominated by peripheral collisions in which the clusters, very surprisingly, are more strongly heated by Xe20+ collisions than by He+ collisions. The appearance size is k=15 for [C ??H??](k)2+.     

氯化钠团簇的形成规律与结合能计算

当离子蒸气冷凝形成团簇时，其结构表现出特定的规律。文中对不同大小不同形状的氯化钠团簇结构与结合能进行了计算，以求揭示离子蒸气冷凝形成团簇的一些规律，并与实验结果进行对照。     

Molecular simulation of LiCl aqueous solutions

Non-primitive LiCl aqueous electrolyte solutions were studied at 1.0, 5.0 and 10.0 M concentrations by molecular dynamics simulations. It was observed that the ion hydration structure is progressively lost with increasing concentration. The ions are aggregated in small clusters at C = 1.0 M. However, at this concentration, two large clusters were detected that are an initial step in an aggregation process. At C = 5.0 M, the highly unstable ion clustering seems to correspond to an intermediary state between low concentration states with poor aggregation and states where the ions are highly aggregated, as observed at C = 10.0 M where almost all the ions are clustered in one cluster. This cluster does not present a crystal-like structure. The high solubility of LiCl in aqueous solutions can consequently be explained as a result of the large radii difference between the anion and the cation that results in the instability of the ionic aggregates, which makes the formation of crystal seeds difficult.     

Local structure of LiCoO(2) nanoparticles studied by Co K-edge x-ray absorption spectroscopy

We have studied the local structure of LiCoO(2) nanoparticles by Co K-edge x-ray absorption spectroscopy as a function of particle size. Extended x-ray absorption fine structure data reveal substantial changes in the near neighbor distances and the associated mean square relative displacements with decreasing particle size. X-ray absorption near edge structure spectra show clear local geometrical changes with decreasing particle size, similar to those that appear in the charging (delithiation) process. The results suggest that the LiCoO(2) nanoparticles are characterized by a large atomic disorder confined to the Co-O octahedra, similar to the distortions generated during the delithiation, and this disorder should be the primary limiting factor for a reversible diffusion of Li ions when nanoparticles of LiCoO(2) are used as cathode material in rechargeable Li ion batteries.     

The influence of ion irradiation on the structure and properties of amorphous carbon films

Presented in this work are the results of investigation of the structure and electrophysical properties of amorphous carbon films. The films were produced by sputtering of graphite by ion beam and usin ion irradiation (E=0–200 eV) during condensation process. The structure of i-C films has been studied by means of transmission electron microscope. The electron diffraction data have been interpretated by employing the calculated interference function of carbon clusters. The structure of V-band was obtained from AES by deconvolution method. Experimental data shows that under ion irradiation the transformation of short range order and electron bonds is an oscillating function of ion energy E. This paper presents a theoretical calculation of tunneling neutralization cross-section of Ar⁺ ions on carbon surface. The process also has an oscillating dependence on ion energy. A significant importance of inelastic processes in carbon phase transformation has been revealed.