The electronic and ionic structures of metal-ammonia solutions

Presently existing data on the properties of liquid metal-ammonia solutions are reviewed critically in relation to physical models and current theory. Emphasis is given to the inter-relation between the electronic properties and the atomic structures of the solutions. The material is organized according to concentration regions characterized by differing electronic and ionic structures. In the very dilute concentration range, 0–10^?3 mole per cent metal (MPM), the solutions behave as ideal electrolytes with solvated electrons and solvated positive ions as the ionic species. Association of these species occurs in the dilute region, 10^?3–10^?1 MPM. We propose that growth of associated complexes into large, metallic clusters occurs in the intermediate region, 10^?1—3 MPM. A metal-non-metal transition or, at lower temperatures, a phase separation takes place in the 3–7 MPM concentration range. We give a simplified theory of the Mott transition for these solutions and explore the inter-relation of the Mott transition, the observed metal-non-metal transition, and the phase separation. The metallic range extends from 7 MPM to saturation at 15 or 20 MPM in the concentrated solutions; we propose a fused-salt-like structure for this region. Suggestions are made for future research.     

A model for the metal-non-metal transition in metal-molten-salt solutions

Summary We outline a theory for the metal-non-metal transition occurring in solutions of alkali metals in molten alkali halides as governed by a balance between the binding of ionic clusters by localized electrons and the excess free energy of an ionic assembly screened by metallic electrons. In the model the transition is driven by the composition dependence of the screening length. The theory is amenable to an analytic solution within the mean spherical approximation when Thomas-Fermi screening is used and the ions are described by charged hard spheres.     

Screening effect of impurities in metals: a possible explanation of the process of cold nuclear fusion

Summary The screening length of the deuterium ion by surrounding electrons in a palladium metal lattice, as estimated using two approaches—viz. the Thomas-Fermi screening theory and the Debye screening theory for plasmas in metal—is found to be less than the interatomic separation of ordinary hydrogen molecules. This has important implications for the possibility of cold nuclear fusion at room temperature, since slight fluctuations in equilibrium conditions may drive the deuterons to fuse together. The relative magnitudes of screening length for the cold nuclear fusion regime and classical hot nuclear regimes (inertial and magnetic confinement) reveal that in the former a comparatively smaller amount of energy is needed to overcome the repulsive Coulomb barrier between two deuterium ions.     

Radiation-induced conductivity of alkali halide crystals in strong electric fields under X-ray and photoexcitation

A study is undertaken into radiation-induced conductivity of alkali halide crystals under X-ray excitation and sequential excitation with X-ray and laser pulses within the absorption band of F-and F ⁻-centers. The basic conduction parameters (concentration and lifetime of carriers upon X-ray and photoexcitation) are estimated. The possible processes responsible for the nonlinearity of the current-voltage characteristics are discussed. It is shown that an increase in the conductivity in strong electric fields may be due to a decrease in the spatial localization of electrons in the conduction band of the insulator.     

Short range order and the metal-insulator transition in disordered systems

The effect of short range order on the electronic density of states, the conductivity, and localization is calculated for a model binary alloy in the simple cubic configuration using a cluster extension of CPA. In the presence of short range order a metal insulator transition takes place as the concentration passes through a critical range.     

Stability patterns of transition metal doped silver clusters: Dopant- and size-dependent electron delocalization

The stability of cationic silver clusters doped with a 3d transition metal atom (Sc, Ti, V, Cr, Mn, Ni, Cu) is investigated by mass spectrometric analysis of fragments resulting from high fluence irradiation of a cluster beam. The mass spectra show enhanced stabilities that correspond to closed shells of valence electrons. Dopant- and size-dependent delocalization of 4s and 3d electrons is discussed based on spherical shell model considerations. Contrary to doped gold clusters, no evidence was found for the existence of 2D electronic shell closures.     

稳态Cu-Zr二十面体团簇电子结构的密度泛函研究

采用第一原理对以Cu为心的低能稳态Cu_nZ_(r13-n)(n=6,7,8,9)二十面体团簇的电子结构进行计算,结果表明:同一化学组分下,以Cu为心的Cu-Zr二十面体团簇中出现的同类原子聚集现象可以增强团簇的稳定性,降低费米能级(EF)上的电子数N(EF),这为低能稳态团簇拥有较小的N(EF)提供了深层次的理论解释.进一步的差分电子密度与Mulliken布居分析得知,Cu-Zr二十面体中共价键与离子键共存,成键态与反键态共存,且团簇在形成时壳层Zr与中心Cu原子是电子的提供者,壳层Cu是电子的获得者.该电荷转移方向是金属玻璃中以Cu为心的Cu-Zr二十面体团簇普遍遵循的规律,不随团簇的化学序参数及化学组分的变化而变化.计算的红外振动谱为实验上准确表征不同二十面体原子团提供了一种新的思路.     

Two-dimensional mesoscopic dusty plasma clusters: Structure and phase transitions

A two-dimensional mesoscopic cluster of “dusty plasma” particles, which can be interpreted as a system of microparticles in an rf gas discharge, is investigated. The ground-state configurations and corresponding eigenfrequencies and eigenvectors are found for clusters of N=22–40 particles in a harmonic confining potential. It is shown that a change in the Debye screening length R of the particle charge in the plasma can cause structural transformations of the ground state of the system, manifested as first-order or second-order phase transitions with respect to the parameter R. The disorder (“melting”) of the clusters is analyzed in detail by Monte Carlo simulation and molecular dynamics. By varying the characteristic range of particle interaction in a cluster, it is possible to modulate its thermodynamic properties and the character of the phase transitions, thereby causing a controlled transition of the system into the fully ordered, orientationally disordered, or fully disordered state. The possibility of dusty plasma clusters coexisting in different states is discussed. Zh. éksp. Teor. Fiz. 116, 1300–1312 (October 1999)     

Quantum Hall effect-insulator transition in the InAs/GaAs system with quantum dots

The InAs/GaAs structures consisting of quantum-dot layers with electronic properties typical of two-dimensional systems are investigated. It is found that, at a low concentration of charge carriers, the variable-range-hopping conductivity is observed at low temperatures. The localization length corresponds to characteristic quantum-dot cluster sizes determined using atomic-force microscopy (AFM). The quantum Hall effect-insulator transition induced by a magnetic field occurs in InAs/GaAs quantum-dot layers with metallic conductivity. The resistivities at the transition point exceed the resistivities characteristic of electrons in heterostructures and quantum wells. This can be explained by the large-scale fluctuations of the potential and, hence, the electron density.     

Au和3d过渡金属元素混合团簇结构、电子结构和磁性的研究

采用基于密度泛函理论的第一性原理方法系统研究了Au与3d过渡元素构成的混合小团簇的结构、稳定性、电子结构及磁性,得到了Au与3d过渡元素构成的混合小团簇的稳定结构.计算结果表明,Au与3d元素可形成大量的低能异构体,特别是有些异构体在结构上极相近,这不同于共价或离子键类型的团簇.与纯过渡金属团簇类似,这类团簇也表现出复杂的磁性.过渡金属元素的磁矩相比体材料而言既有增强的、也有减弱的,与轨道的交换劈裂密切相关.对于基态构型,AuCr₂,Au₂Cr_{2关键词： 密度泛函理论 第一性原理方法 团簇 电子结构}     

Electronic and magnetic properties of semiconducting nanoclusters and large organic molecules: Features interesting for spintronics

Spin properties of single-doped and single-electron charged nano-systems having an odd number of electrons are studied. Starting from an expression for quasiparticle energies in the GW approximation, a simple analytical expression for the spin-splitting of an electron spectrum in such system is derived. First-principles calculations by the DFT–GGA, Hartree-Fock, GW- and hybrid functional methods, which were performed for the silicon clusters and metal phthalocyanine molecules of 1 nm diameter, support this analytical consideration. They show that the spin-splitting energy calculated by the DFT–GGA method is about one order lower, than the results obtained with the methods based on the many-electron theory. A large value of spin-splitting in investigated nano-systems, which is typically of several eV, has an origin in strong localization of electrons and weak screening of exchange interaction. A possible use of this effect in spintronic applications is discussed.     

Radiative transition mechanisms in metal clusters

Experimental data on the absorption of radiation by cold lithium, potassium, and silver clusters and on the emission of radiation by hot niobium and tungsten clusters are analyzed within the scope of two interpretive schemes of radiative transitions in clusters. The first scheme comprises plasmon model of light absorption by valence electrons of metal clusters. The second scheme treats radiative transitions in metal clusters as transitions of valence electrons interacting with surrounding electrons and atomic cores. The experimental data exhibit better agreement with the second interpretation. Zh. éksp. Teor. Fiz. 116, 1903–1911 (December 1999)     

Chiral structures and tunable magnetic moments in 3d transition metal doped Pt6 clusters

The structural, electronic, and magnetic properties of transition metal doped platinum clusters MPt6 （M=Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn） are systematically studied by using the relativistic all-electron density functional theory with the generalized gradient approximation. Most of the doped clusters show larger binding energies than the pure Pt7 cluster, which indicates that the doping of the transition metal atom can stabilize the pure platinum cluster. The results of the highest occupied molecular orbital （HOMO） lowest unoccupied molecular orbital （LUMO） gaps suggest that the doped clusters can have higher chemical activities than the pure Pt7 cluster. The magnetism calculations demonstrate that the variation range of the magnetic moments of the MPt6 clusters is from 0 μB to 7 μB, revealing that the MPt6 clusters have potential utility in designing new spintronic nanomaterials with tunable magnetic properties.     

Conditions for generation of X-ray cherenkov radiation during motion of charges in realistic media

The influence of the spatial distribution of electrons, atoms, and nuclei in condensed media on a medium’s susceptibility and on the conditions for the formation of short-wavelength Cherenkov radiation are considered. It is shown that taking into account the inhomogeneous (atomic and electronic) structure of material media in which fast charged particles travel leads to a change in the effective susceptibility and permittivity in the X-ray range, as compared with cases of model homogeneous media with the same average concentration of electrons. The influence of the distribution functions of electrons and nuclei in a target on the conditions for Cherenkov radiation generation and its parameters and on the threshold energy of fast charged particles required to generate such radiation is studied. It is shown that the function of the spatial distribution of electrons and nuclei in a target affects the conditions for generating laser radiation in the X- and λ-ray ranges (on the problem of X- and λ-ray lasers). The obtained results show that using the Fresnel approximation in the X-ray range is insufficiently justified and can lead to significant errors.     

Electrical current in nanoelectronic devices

In ultra-small electronic devices of the next generations the semiclassical model of electron motion in a periodical lattice between collisions turns out to be inadequate because the electron spread has magnitude order of the size of the ultra-small electronic device. In this Letter we consider the basic conceptual framework regarding how the length scale of the electrical device influences the transport behavior of the electrons between collisions and the electrical current. By taking into account the interference effects we obtain a very basic model for electrons transport, where the density current peak is given as function on the ratio between the thermal de Broglie wavelength and the lattice period. This result could be also useful in order to understand the basic effect of the insulator/metal transition.     

高温有机超导的可能性

本文讨论了高温有机超导所遇到的两个主要问题。首先,从描写有机分子电子态的Bloch波函数出发,利用微扰论,证明了有机分子中的Coulomb场由于可移动电子的存在仍然将产生某种屏蔽作用,其屏蔽长度的平方与Fermi能级处的态密度成反比。其次,利用包含σ键压缩能的分子轨道理论,得到了象聚二苯(polyacenacene)这类有机分子有可能不发生Peierls畸变。由此表明,在其他条件满足时,在某些有机分子中出现超导态是完全可能的,同时也指出了有机材料在Fermi能级处具有较大的态密度似乎是实现Little有机超导设想的关键。     

Electron-forbidden energy gap of hydrogen in a wide pressure interval

A simple model is used for estimating the bottom energy of the electron conduction band and the electron-forbidden gap energy. It is shown that electrons in liquid hydrogen are localized not in electron bubbles, as was considered previously, but in molecular negative ions surrounded by voids about 0.5 nm in radius. The conductivity of fluid hydrogen at not very high pressures is connected to transfer of positively charged clusters and negatively charged bubbles. As the pressure and density increase, molecular dissociation occurs and electron localization on atoms becomes more favorable, also with the creation of a void around atomic negative ions. At a sufficiently high concentration of atoms, the probability of tunnel transition of an electron from one atom to another becomes close to unity, the energy level of the negative ion degenerates in the band, and the conductivity is caused by the transfer of these quasifree electrons. It is supposed that this charge transfer mechanism may play an important role in the region of fluid hydrogen metallization.     

团簇ConAgm (n +m =13)表面吸附C2H4的第一性原理研究

基于密度泛函理论的第一性原理计算方法,本文对ConAgm(n+m=13)团簇的几何结构进行优化后,研究了C2H4分子在这类团簇的表面吸附行为,讨论了团簇的平均结合能、二阶能量差分、稳定性、DOS以及吸附前后键长的变化情况。结果表明,C2H4在团簇top位的吸附主要为物理吸附,而在face位和bridge位的吸附主要为化学吸附。吸附后,C2H4@Ag13的稳定性高于C2H4@Co13,且在face位吸附时C2H4@Co2Ag11的结构最为稳定。随着Co原子数的增加,团簇中原子间成键能力减弱,而d电子轨道则呈现出较强的相互作用,并导致其向能量相对高处发生转移     

The metal-insulator transition and the phase transition in metal-ammonia solutions

The ground state of impurity metal (sodium) atoms in liquid ammonia close to the solvated state of the free electrons is considered. It is shown that the critical solubility point lying on the metal side of the metal-insulator transition is determined by the Coulomb interaction between the ions and electrons in the overlapping impurity states, classically accessible spheres of which form an infinite percolation cluster. The percolation conductivity via the impurity states is estimated. The estimate agrees with the experimental data near the critical solubility point. Zh. éksp. Teor. Fiz. 111, 938–948 (March 1997)