Critical concentration for metallization of doped germanium and silicon

An elementary model for the metal-non metal transition in n-type Ge and Si is considered. The model is based on recent theoretical work on electron-hole droplets in illuminated semiconductors. The energy of the metallic phase is computed from experimentally known values of the conduction band effective masses and the background dielectric constant. The critical concentration is determined approximately by comparing the energy of the metallic phase with the energy of an isolated donor atom (a bound electron-impurity ion pair). The theoretical estimates of the critical concentration agree in order of magnitude with experiments. The trend in chemical shifts is reproduced.     

掺杂元素对Mg2NiH4稳定性影响的第一性原理研究

本文采用基于密度泛函理论(DFT)的第一原理赝势平面波(PW-PP)方法,计算了低温相Mg2NiH4和(Mg2Ni,X)H4(X=Ag, Al, Ti或Zr)的生成热及电子结构,分析了掺杂元素对Mg2Ni氢化物稳定性的影响. 结果表明,掺杂导致了合金氢化物生成热的绝对值降低,合金氢化物的稳定性下降,且发现掺杂元素电负性越大,氢化物越不稳定. 从电子态密度图和Mulliken布居数分析知道,掺杂后合金氢化物释氢能力增强的主要原因在于Ni-H之间的成键减弱,以及掺杂元素诱导费米能级EF处电子数浓度N(EF)的增加.     

过渡金属氮化物中单原子固溶和力学性能的第一性原理研究

基于密度泛函理论(DFT)的第一性原理,计算Si原子在Ti族和V族氮化物中以及B、C和Ge原子在TiN晶体中固溶的稳定结构,讨论置换型和间隙型固溶的低能量稳定结构与晶体间距的关系,研究金属氮化物和固溶原子固溶结构的力学性能.结果表明:Si原子在TiN、ZrN、HfN和TaN晶体中固溶以及Ge原子在TiN晶体中固溶情况为,单原子不进入对应过渡金属氮化物晶体中形成间隙固溶或置换固溶,随着晶体间距离变化单原子可以在晶体之间形成间隙固溶或置换固溶;Si原子在NbN以及B原子在TiN晶体中可以实现间隙固溶,而不能形成置换固溶;Si原子在VN和C原子在TiN晶体中固溶结构形式均为置换固溶.单原子固溶形成低能量置换型固溶体和间隙型固溶体的弹性常数、体模量和剪切模量均低于原过渡金属氮化物的对应值.     

掺杂元素对Mg2NiH4稳定性影响的第一性原理研究

本文采用基于密度泛函理论(DFT)的第一原理赝势平面波(PW-PP)方法,计算了低温相Mg2NiH4和(Mg2Ni,X)H4(X=Ag, Al, Ti或Zr)的生成热及电子结构,分析了掺杂元素对Mg2Ni氢化物稳定性的影响. 结果表明,掺杂导致了合金氢化物生成热的绝对值降低,合金氢化物的稳定性下降,且发现掺杂元素电负性越大,氢化物越不稳定. 从电子态密度图和Mulliken布居数分析知道,掺杂后合金氢化物释氢能力增强的主要原因在于Ni-H之间的成键减弱,以及掺杂元素诱导费米能级EF处电子数浓度N(EF)的增加.     

Compressibility of hydrogen in Ni and Re hosts at pressures to 123 GPa

Abstract

Ni-H and Re-H binary systems have been studied at room temperature by X-ray diffraction in a diamond-anvil cell. The formation of the hydrides NiH and ReHo.4 with no change in the types of the host metal lattices was observed through the expansion of the host lattices. No structure changes were observed in the metal sub-lattice of either hydride under increasing pressure and the equations of state have been obtained to 123GPa. The difference in the partial hydrogen volume as a function of pressure between the Ni-H and Re-H systems can be understood with reference to the behaviour of conduction electrons. The pressure dependence of the partial hydrogen volume in these hydrides supports the hypothesis of the apparent common-volume behaviour of hydrogen in a metallic environment.     

Surface vibration correlation with d-electron (hole) per atom ratio (d-bandfilling) in CO chemisorption on supported transition metal particles: Dominance of hund's rule and d-electron degeneracy in real supported catalysts

The findings of Guerra and Schulman (ref.1) of a correlation between force constant of metal-CO chemisorbed species (admolocules) with the number of d-holes per atom (1-number of d-electrons per atom, or d-bandfilling) of the transition metal particle (supported) surface is treated using the ten-fold degenerate Hubbard (ref.2) (TDHM) and Anderson (TDAM) (ref.3) models developed for magnetic and Mott metal-insulator transition problems in transition metals, alloys and compounds. Their experimental finding that via infrared spectroscopy on the CO adsorbed species (admolecule) bond, the infrared surface vibrational frequency, CO bond order and CO bond force constant were nearly linear versus the number of d-holes per transition metal surface atom is easily explained via the TDHM and TDAM via their inherent d-bandfilling dependent (alloy specific) Coulomb and exchange enhanced coupling strength between d-electrons or d-holes (ref.4). Even the Fulde (ref.5) correction to the number of d-electrons (holes) per $\text{surface}$ atom as a function of transition metal particle size does not change the excellent agreement, but merely renormalizes the measured functional properties versus d-hole per atom ratio for a suite of equally fine sized transition metal particles. So it seems that in admolecule chemisorption (at least for CO) the degenerate electronic properties of the surface dominate the vibrational and bonding properties of the admolecular species rather completely.     

FPT-CNDO/INDO化学屏蔽常数计算方法及其在Mo和Co化合物中的应用

Semi -empirical molecular orbital methods within the framework of the finite perturbation theory , the FPT-CNDO/INDO methods , which consist of the FPT-CNDO/2 and FPT-INDO methods, are set up for the study of chemical shielding in transition metal compounds, and a corresponding computational program is developed on VAX 11/785 computer to establish a theoretical study of the transition metal chemical shielding by quantum chemistry methods. Application of the methods has been carried out in the calculation of 95Mo chemical shielding constants of mononuclear precursors [MoOnS4-n]2-(n=0-4). With the standard CNDO/INDO parameters a linear regression was obtained between the calculated results and the corresponding experimental data:δcal=(0.8345 δexp-43.83)ppm, with a correlation coefficient of 0.999. Investigation on the calculated electronic configuration confirms that in [MoOnS4_n]2- (n=0-4)95Mo chemical shifts are dominated by the d-orbital paramagnetic contribution arising from the d-d transition. Appl     

The catalytic activity of chemisorbed oxygen and carbon monoxide species on palladium and related metals investigated using SCF-Xα-SW calculations

Theoretical calculations of the electronic structure of small clusters modelling the adsorption of carbon monoxide on nickel and palladium and the adsorption of oxygen on palladium and platinum have been carried out using the SCF-Xα-SW method. Our results for the carbon monoxide-nickel clusters are in good agreement with earlier work. Comparing the carbon monoxide-nickel with the carbon monoxide-palladium results, suggests that the ordering of CO-derived cluster orbitals is the same in both cases but that the relative shifts are much different. In addition, the oxygen atom participates more significantly in the cluster containing palladium. An analysis of optical transition energies for Ni₅CO and Pd₅CO clusters is given and discussed in terms of experimental data regarding photodesorption of carbon monoxide. In the case of oxygen atoms in platinum and palldium clusters, we have used two different M₅O geometries: one in which the five metal atoms are in a single plane and oxygen is directly over a single metal atom (Type A) and a second in which the oxygen atom is coordinated to four sur face metal atoms and is directly over a metal atom in the second layer (Type B). The levels calculated for the Pd50 type B cluster are in good agreement with available UPS data. Significant differences in type A and type B clusters are noted for palladium. The results can be correlated with experimental Auger spectroscopic and kinetic data. In particular, the type A oxygen cor relates well with an experimentally observed very reactive species, while type B oxygen cor relates well with a quite unreactive species. These two types also correlate with two species observed by Auger spectroscopy.     

Plasmon-phonon mechanism of nonradiative transition 2S 1/2 → 2P 1/2 in grazing scattering of a hydrogen atom at the surface of a solid

The probability of nonradiative transition 2S _1/2 ?? 2P _1/2 in the case of grazing scattering of a hydrogen atom with an energy on the order of 1 keV at an Au and LiF surface is calculated in the semiclassical theory of nonadiabatic transitions. The transitions are induced by the interaction of the atom with the fields of surface plasmons and optical phonons, respectively. A formalism is developed which makes it possible to exceed the approximation based on the method of electrical images of charges. The value of the probability of scattering at LiF is high enough for experimental observation of the effect. The probability of this transition is determined for the motion of the atom parallel to the metal surface.     

Magnetic properties in transition-metal-doped gold clusters: M@Au6 (M = Ti, V, Cr)

The electronic structure and magnetic properties in a series of transition-metal-doped Au clusters, MAu6- (M = Ti, V, Cr), are investigated experimentally using photoelectron spectroscopy (PES) and density functional calculations. PES features due to the impurity atoms and the host are clearly observed. It is found that all the MAu6- and MAu6 clusters possess a planar structure, in which the transition metal atom is located in the center of an Au6 ring and carries large magnetic moments (2, 3, and 4 muB for MAu6, M = Ti, V, and Cr, respectively).     

A first-principles study on the electronic structure of one-dimensional [TM(Bz)]∞ polymer (TM= Y, Zr, Nb, Mo, and Tc)

A systematic density functional theory (DFT) study has been performed to investigate the electronic and magnetic properties of one-dimensional sandwich polymers constructed with benzene (Bz) and the second-row transition metal (TM = Y, Zr, Nb, Mo, and Tc). Within the framework of generalized gradient approximation (GGA), [Tc(Bz)]_∞ is a ferromagnetic half-metal, and [Nb(Bz)]_∞ is a ferromagnetic metal. With the on-site Coulomb interaction for 4d TM atoms being taken into account, [Tc(Bz)]_∞ keeps a robust half-metallic behavior, while [Nb(Bz)]_∞ becomes a spin-selective semiconductor. The stability of the half-metallic [Tc(Bz)]_∞ polymer is discussed based on magnetic anisotropy energy (MAE). Compared with 0.1 meV per metal atom in [Mn(Bz)]_∞, the calculated MAE for [Tc(Bz)]_∞ is 2.3 meV per metal atom. Such a significantly larger MAE suggests that Tc(Bz)]_∞ is practically more promising than its first-row TM equivalent.     

Theoretical study of magnetic ordering and electronic properties of AgxAl1−x N compounds

Ferromagnetic ordering of silver impurities in the AlN semiconductor is predicted by plane-wave ultrasoft pseudopotential and spin-polarized calculations based on density functional theory (DFT). It was found that an Ag impurity atom led to a ferromagnetic ground state in Ag_0.0625Al_0.9375N, with a net magnetic moment of 1.95 μ_B per supercell. The nitrogen neighbors at the basal plane in the AgN₄ tetrahedron are found to be the main contributors to the magnetization. This magnetic behavior is different from the ones previously reported on transition metal (TM) based dilute magnetic semiconductor (DMS), where the magnetic moment of the TM atom impurity is higher than those of the anions bonded to it. The calculated electronic structure band reveals that the Ag-doped AlN is p-type ferromagnetic semiconductor with a spin-polarized impurity band in the AlN band gap. In addition, the calculated density of states reveals that the ferromagnetic ground state originates from the strong hybridization between 4d-Ag and 2p-N states. This study shows that 4d transition metals such as silver may also be considered as candidates for ferromagnetic dopants in semiconductors.     

Ab initio study of sodium intercalation into metal oxides

Using the full-potential linearized augmented plane wave (FP-LAPW) method, we have studied the effect of chemistry on the average intercalation voltage (AIV) caused by the Na ions intercalating into transition metal oxides. The effect of transition metal was systematically studied by varying M=Co, Ni and Mn in NaMO₂ and fixing the α-NaFeO₂ layered structure. The effect of the guest atoms into the host material is discussed in terms of the structural and electronic properties. Comparatively to Li intercalation, a significant electron transfer towards transition metal was found. This observation suggests that the transition metal contribute to the AIV determination and confirms the common assumption that intercalated electron reduces M⁴⁺ to M³⁺.     

H,O原子在过渡金属表面吸附能的规则性

用Allan的简化d带模型描叙过渡金属的表面电子态,用广义相移法计算吸附原子在表面的吸附能,结果表明,不仅很好地描绘了H,O在一个周期的过渡金属表面吸附能的变化趋势,而且所算得的吸附原子感应的分离能级也同紫外光发射谱的实验符合得很好;同时还指出,简单气体在过渡金属表面的吸附能呈现规则性变化主要决定于费密能级E_F与吸附原子的有效能级ε_a之差(E_F-ε_a),其次是转移矩阵元ν和能带宽度w_b。 关键词：     

Self-organized layered hydrogenation in black Mg2NiHx switchable mirrors

In addition to a mirrorlike (Mg2Ni) and a transparent (Mg2NiH4) state, thin films of Mg2NiHx exhibit a remarkable black state with low reflection over the entire visible spectrum, essentially zero transmission and a low electrical resistivity. Such a black state is not explicable for a homogeneous layer since a large absorption coefficient always yields substantial reflection. We show that it results from a self-organized and reversible double layering of metallic Mg2NiH0.3 and semiconducting Mg2NiH4.     

NiH2分子的结构及其势能函数

应用群论及原子分子反应静力学方法推导了NiH2分子基态的电子态及其离解极限,在MP2/6-311G水平上,优化出NiH2(3Δg)分子稳定构型为D∞h,其平衡核间距Re=0.157 3 nm、∠HNiH=180.00°,同时计算出振动频率:对称伸缩振动频率ν1=2 000 cm-1,弯曲振动频率ν2=721 cm-1和反对称伸缩振动频率ν3=1 875 cm-1.在此基础上,使用多体项展式理论方法,导出了基态NiH2分子的全空间解析势能函数,该势能函数准确地再现了NiH2(D∞h)平衡结构.     

The electronic and magnetic properties of the 3d transition metal intercalates of TiS2

The introduction of 3d transition metals (M) into the van der Waals gaps between the weakly coupled layers of transition metal dichalcogenides TX₂ (T:transition metal, X:chalcogen) produces an interesting family of intercalation compounds, M _x TX₂, the physical properties of which are different from those of the host TX₂ matrix because of ‘host-guest’ interactions. In this article we shall review the salient features of the M _x TiS₂ family with the simple 1T-CdI₂ type layered structure, which have been extensively studied by structural, transport, specific heat and lattice dynamic, magnetic and photoemission spectroscopic measurements. In contrast with the previously reported series of intercalation complexes of the Group V transition metal dichalcogenides, a characteristic of the M _x TiS₂ materials is strong hybridisation between the guest atom M 3d orbitals and the host Ti 3d and S 3p orbitals, leading to changes in the Fermi energy E _F of the conduction band, the density of states at E _F and various types of magnetic orderings. These properties are understood in terms of an itinerant electron or band picture for the intercalant, rather than a rigid band or localised model.     

A first-principles study on the electronic structure of one-dimensional [TM(Bz)]∞ polymer (TM= Y, Zr, Nb, Mo, and Tc)

A systematic density functional theory (DFT) study has been performed to investigate the electronic and magnetic properties of one-dimensional sandwich polymers constructed with benzene (Bz) and the second-row transition metal (TM = Y, Zr, Nb, Mo, and Tc). Within the framework of generalized gradient approximation (GGA), [Tc(Bz)]_∞ is a ferromagnetic half-metal, and [Nb(Bz)]_∞ is a ferromagnetic metal. With the on-site Coulomb interaction for 4d TM atoms being taken into account, [Tc(Bz)]_∞ keeps a robust half-metallic behavior, while [Nb(Bz)]_∞ becomes a spin-selective semiconductor. The stability of the half-metallic [Tc(Bz)]_∞ polymer is discussed based on magnetic anisotropy energy (MAE). Compared with 0.1 meV per metal atom in [Mn(Bz)]_∞, the calculated MAE for [Tc(Bz)]_∞ is 2.3 meV per metal atom. Such a significantly larger MAE suggests that Tc(Bz)]_∞ is practically more promising than its first-row TM equivalent.      

A route to transparent bulk metals

Hypothetical compounds based on a sapphire host are investigated with respect to their structural as well as electronic features. The results are obtained by electronic structure calculations within density functional theory and the generalized gradient approximation. A quarter of the Al atoms in Al₂O₃ is replaced by a 4d transition metal M ion, with d⁰ to d⁹ electronic configuration. We perform structure optimizations for all the compounds and analyze the electronic states. Due to the sizeable band gap of the Al₂O₃ host, we can identify promising candidates for transparent bulk metals. We explain the mechanisms leading to this combination of materials properties. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Doppler-free two-photon spectroscopy

We describe atomic transitions where two or more photons are simultaneously absorbed by an atom or a molecule (without any intermediate resonant level). We show theoretically and experimentally the possibilities of these transitions for numerous high-resolution spectroscopic studies. The principle of the method is discussed: the Doppler broadening is suppressed in two-photon transitions if the atoms are irradiated by two laser beams travelling in opposite directions, because the Doppler shift in one wave cancels that in the other. A generalization is made for multiphotonic transitions. Calculations of the multiphotonic transition probability are summarized and their hypotheses specified: one deals with line shape and orders of magnitude in practical conditions. The problem of light shifts is also discussed. A typical experimental set-up with a cw dye laser is described in detail. Typical recordings of two-photon transitions are given; they show line widths smaller than 4 MHz (on a Doppler width of 2000 MHz). Other experiments show the possibility of increasing the transition probability by using two lasers with slightly different wave lengths. One experiment with a three-photon Doppler-free transition is also described. In conclusion, we make a brief comparison with the saturated absorption technique.