Halogen adsorption on Fe(100): I. The adsorption of Cl2 studied by AES,LEED, work function change and thermal desorption

The initial sticking probability of chlorine on Fe(100) at room temperature is calculated to be 0.13, and there is evidence to suggest that the chlorine adsorbs into a short lived mobile precursor state above the surface. The work function change, Δφ, is proportional to coverage and reaches a maximum value of 1.43 eV at saturation. At this coverage a c(2 × 4) LEED pattern is formed. On heating, chlorine is lost from the surface, but the mechanism is such that no detectable loss is incurred at a constant elevated temperature. The c(2 × 4) pattern is shown to be a coincidence structure formed from a $\text{(}\text{1}\text{2}\text{3}\text{?1}\text{2}\text{3}\text{)}$ net of chlorine atoms on the Fe(100) substrate. This structure is a special case of the more general $\text{(}\text{1}\text{2}\text{tan}\text{α}\text{?1}\text{2}\text{tan}\text{α}\text{)}$ structure formed at lower concentrations of chlorine. The c(2 × 4) is formed when α = 56.31°, which gives the chlorine atoms a hard sphere diameter of 0.345 nm and a concentration of 0.75 atoms per four-fold site.     

An equivalent cores calculation of solid-state and adsorbate shifts in X-ray photoelectron spectroscopy

An equivalent cores model is used to calculate the observed binding energy shifts in the X-ray photoelectron spectra of atoms when bonding to form a solid phase. Good agreement is found with experimental data both for the formation of elemental metals and for the adsorption of gases on metal surfaces.     

Electron binding energies in the study of adsorption by photoelectron spectroscopy: The reference level problem

There has been much discussion in the literature concerning the definition of a suitable reference level for electron binding energies in solids and adsorbed species. The reference level in molecular photoelectron spectroscopy is the vacuum level at infinity; and, in order to calculate the total energy of the system, it is also the appropriate reference level for electron binding energies in solids. We show that for solids and adsorbates the vacuum level is not a chemically useful reference level. This is because the absolute binding energy is affected by electrostatic potentials which are unrelated to the local chemical bonding. It is concluded that there is no experimental energy level, to which adsorbate binding energies can be referenced, which allows one to make an absolute measurement of binding energy shifts due to surface interaction. Approaches to obtaining chemically meaningful binding energies from the photoelectron spectra of adsorbates are discussed.     

XPS study of the exchange-splitting in the s-levels of Mn and R in RMn2Si2 (R = La to Nd,Sm and Gd)

Exchange (or multiplet) splitting, ΔE_s of the 3s core-level of Mn in RMn₂Si₂ (R = La to Nd, Sm and Gd) has been observed using XPS technique. The measured value of ΔE_s is used to determine the magnetic moment on Mn ion in RMn₂Si₂. ΔE_s has also been measured for the 4s and 5s levels of R in RMn₂Si₂ and it is found that the value of ΔE_s increases with increase in the number of unpaired spins (La to Gd).     

Spin‐polarized electron gas in Co2M Si/SrTiO3 (M = Ti,V, Cr,Mn, and Fe) heterostructures

Spin‐polarized density functional theory is used to study the TiO₂ terminated interfaces between the magnetic Heusler alloys Co₂Si (M = Ti, V, Cr, Mn, and Fe) and the non‐polar band insulator SrTiO₃. The structural relaxation at the interface turns out to depend systematically on the lattice mis‐ match. Charge transfer from the Heusler alloys (mainly the M 3d orbitals) to the Ti d_xy orbitals of the TiO₂ interface layer is found to gradually grow from M = Ti to Fe, resulting in an electron gas with increasing density of spin‐polarized charge carriers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Variation of the electronic structure in systematically synthesized Sr2MO4 (M = Ti, V, Cr, Mn, and Co)

We have systematically synthesized single-crystalline thin films of layered perovskites Sr2MO4 (M = Ti, V, Cr, Mn, and Co) which cannot be obtained in a form of bulk crystal apart from M = Mn. The two-dimensional electronic structure of these M4+ oxides, ranging from a correlated insulator to a ferromagnetic metal, has been investigated by using their optical conductivity spectra with polarizations E is perpendicular to c and E is parallel to c, which reveal systematic variation of the correlated charge gap, Mott-Hubbard gap, or charge-transfer gap. Temperature dependence of the gap-transition spectra is argued in the light of possible spin and/or orbital ordering.     

Electronic structure and half-metallicity in Heusler alloys Fe2YB (Y=Ti, V, Mn, Cr)

The electronic structure and magnetic properties of B-based Heusler alloys Fe₂YB (Y=Ti, V, Cr and Mn) have been studied theoretically. These alloys are all ferrimagnets except for Fe₂VB. The latter has 24 valence electrons and is a paramagnetic semimetal. Fe₂CrB is predicted to be half-metals at equilibrium lattice constant. The spin polarization of Fe₂MnB is also quite high. The calculated total moments are 1.00 μ_B for Fe₂CrB and 2.04 μ_B for Fe₂MnB. In Fe₂CrB and Fe₂MnB, the total moments are mainly determined by the partial moment of Cr or Mn. The Fe moment is relatively small and antiparallel to that of Cr or Mn. Under uniform lattice distortion, the half-metallicity of Fe₂CrB is more stable than Fe₂MnB, which is related to the detailed DOS structure of them near E_F.     

Preparation and crystallographic data of the pyrochlores Gd2MSbO7 (M = Cr,Mn, Fe,In)

Polycrystalline Gd₂MSbO₇ (M =Cr,Mn,Fe,In) have been prepared from M₂O₃ (M = Cr, Fe, In), Mn metal and Sb₂O₃ at different temperatures above 1470 K. Gd₂MSbO₇ (M = Cr, Mn,Fe,In) are cubic, pyrochlore-type compounds, space group Fd3̄m (No. 227), Z = 8, a values varying from 10.266 (1) (M = Cr) to 10.486 (1) Å (M = In). For Gd in 16(c), M and Sb at random in 16(d) sites, oxygen atoms in 8(a) and 48(?) positions and x, oxygen positional parameter, equal to 0.412 (M = In) up to 0.425 (M = Mn), origin at center (3̄m), R values from 0.032 (M = In) to 0.041 (M = Mn) are obtained. X-ray powder diffraction data and interatomic distances are given.     

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}     

Anomalies in the behavior of the non-stoichiometric systems ZrMn2T0.8 (T = Mn,Fe, Co,Ni and Cu)

Unit cell dimensions and hydriding characteristics of the non-stoichiometric systems ZrMn₂T_0.8, with T = Mn, Fe, Co, Ni and Cu have been determined. Hydrides of these systems show plateau pressures at 25 C which vary in a systematic way with the atomic number of T, ranging from 0.3 (for T = Fe) to 4 atm (for T = Co). All of these plateau pressures are much greater than that of the hydride of stoichiometric ZrMn₂. There is a “Cobalt Effect” in that the plateau pressure of ZrMn₂Co_0.8 hydride is extraordinarily high and, moreover, the lattice dimensions of ZrMn₂Co_0.8 are small compared to ZrMn₂ and the other ternaries. The origin of the Co effect is as yet unclear. It may originate with the particulars of the site occupancies or special metallic bonding effects.     

Magnetism and hyperfine interactions of Fe, Eu, Gd, Dy, Er and Yb in RM4Al8 compounds (R = rare earth or Y, M = Cr, Mn, Fe, Cu)

Mössbauer and magnetic susceptibility studies of sixty tetragonal RM₄Al₈ compounds (R = 4f, M = 3d element), show a wide variety of magnetic phenomena in the behaviour of 3d transition elements. The rare earths order antiferromagnetically at temperatures below 10–30 K in all compounds. The 3d elements, however, all behave differently. Fe in RFe₄Al₈ has a localized moment (effective moment of 4.4 _μB) and orders independently of the rare earth sublattice. Mn in RMn₄Al₈ has also a localized moment (1 _μB) but orders only when the rare earths order. Cr in RCr₄Al₈ has no moment of its own, but it has an induced moment (.1 _μB) by its magnetic rare earth neighbours. Cu in RCu₄Al₈ is nonmagnetic. The Mössbauer studies of ¹⁵¹Eu, ¹⁵⁵Gd, ¹⁶¹Dy, ¹⁶⁶Er, ¹⁷⁰Yb and a ⁵⁷Fe probe yield all hyperfine interaction parameters including the orientation of the hyperfine field relative to the crystallographic c-axis. In addition, the studies yield the Ce, Eu and Yb valencies in the various compounds. Eu in EuFe₄Al₈ and in EuMn₄Al₈ and Yb in YbCr₄Al₈ are in a mixed valent state.     

K7[P2Mo4W13M(H2O)O61]及其有机复合材料的合成及光谱研究

用降解法制得了Dawson结构铬、铁取代的磷钼钨酸钾,并将其与溴化(E)-N-丁基-4-(2-(4-二甲氨基苯基)乙烯基)吡啶反应制备了有机复合材料.通过元素分析和TG-DTA确定了配合物的组成分别为K7[P2Mo4W13M(H2O)O61](M=Cr(1),Fe(2))和(C19H25N2)6K3[P2Mo4W13MO62](M=Cr(3),Fe(4)).利用红外光谱、紫外-可见光谱、固体漫反射紫外-可见-近红外光谱、X射线光电子能谱以及荧光光谱对上述化合物进行了表征,并研究了复合材料中无机与有机组分间的相互作用及其荧光性质.     

轨道序和巡游性对尖晶石结构钒氧化物AV2O4 (A = Mn,Fe, Co) 物性影响的研究

在尖晶石钒基氧化物AV_2O_4中,因为自旋阻挫、轨道序、巡游性等独特的内禀属性间存在着相互合作和竞争,所以该体系常常表现出复杂而有趣的物理现象。通过对A位磁性离子的调控,我们详细研究该体系中不同物性的起源,比如磁相变与结构相变的不同起因,局域和巡游电子的交叉行为等等。我们以Mn_(1-x)Co_x V_2O_4和Fe_(1-x)Co_x V_2O_4体系为研究对象,通过变温X射线衍射、磁化率、比热和中子散射等测试手段,结合第一性原理计算,对其物性起源进行了详细的研究。我们发现:(i)在低Co2+离子掺杂时,体系受到局域V~(3+)离子以及A位Fe~(2+)离子的轨道序作用,往往会在磁有序附近伴随着结构相变的出现,以至于弱化体系中钒离子独立形成的四面体造成的几何阻挫。这也说明Co~(2+)离子低掺杂下,该体系有着强的自旋–晶格耦合;(ii)在高Co~(2+)离子掺杂时,由于巡游性的增强,轨道序的弱化,JAB交换相互作用增强,体系也表现出明显的磁各向同性。因此磁相变温度向更高的温度移动,而结构相变温度向低温移动甚至消失。     

Ab initio prediction of half-metallic ferromagnetism in Zn(TM)O2 (TM=Cr,Mn, Fe,Co, Ni) compounds

From the results of first principles tight-binding linear muffin-tin orbital (TB-LMTO) calculations, half-metallic ferromagnetism is proposed in Zn(TM)O₂ with a chalcopyrite structure. The calculated electronic and magnetic property shows that consistent with the integer value for the total magnetic moment, half metallicity is obtained for ZnCrO₂, ZnMnO₂, ZnFeO₂, ZnCoO₂ and ZnNiO₂. A careful analysis of the spin density reveals the ferromagnetic coupling between the p–d states and the cation dangling-bond p states, which is believed to be responsible for the stabilization of the ferromagnetic phase. The calculated heat of formation, bulk modulus and cohesive energy are reported.     

Full-Heusler合金X2YGa(X=Co,Fe,Ni;Y=V,Cr,Mn)的电子结构、磁性及半金属特性的第一性原理研究

利用基于密度泛函理论的全势线性缀加平面波方法,结合广义梯度近似,对full-Heusler X₂YGa(X=Co,Fe,Ni;Y=V,Cr,Mn)合金的电子结构、磁性及半金属特性进行了研究,并讨论了自旋-轨道耦合作用对它们的影响.计算结果表明,自旋-轨道耦合作用对full-Heusler X₂YGa(X=Co,Fe,Ni;Y=V,Cr,Mn)合金的电子结构,磁性与半金属特性的影响很小. 当未考虑自旋-轨道耦合作用时,Co₂VGa,Co₂CrGa,和Fe₂CrGa合金为半金属或准半金属铁磁体,加入自旋-轨道耦合作用后体系的自旋极化率将降低1%左右, 它们依然保持很高的自旋极化率.Fe₂MnGa,Co₂MnGa,Ni₂CrGa和Ni₂MnGa合金为一般铁磁体,Fe₂VGa和Ni₂VGa合金为顺磁体. 关键词： 半金属特性 自旋-轨道耦合 Heusler合金 全势线性缀加平面波方法(FLAPW)     

Synthetic metals based on tetramethyltetraselenafulvalene(TMTSF): Varied anisotropy in the low temperature (125K) structures of (TMTSF)2X,X=C104-, PF6-, and AsF6-.

The low temperature (125K) X-ray crystal structures of (TMTSF)₂X, X=C10₄^-, PF₆^-, and AsF₆^- reveal decreases in the intermolecular interand intrastack Se-Se contact distances upon cooling (298K to 125K) which are highly anisotropic and different from one salt to another. The changes in the interstack distances, which are normal to the stacking direction, are approximately twice those involving intrastack Se-Se interactions. These observations establish that the anisotropic structural changes which accompany decreased temperature are common to numerous (TMTSF)₂X radical cation conducting salts.     

A2( MoO4)3(A=Al,Cr,Fe)结构与相变的Raman光谱研究

用XRD、Raman光谱和DSC研究了Al2 (MoO4)3、Cr2( MoO4)3和Fe2 (MoO4)3的结构与相变.Al2(MoO4)3、Cr2 (MoO4)3和Fe2 (MoO4)3在室温下为单斜相,分别在483 K、673 K和783 K附近转变为正交相.发现MO4四面体的对称和反对称伸缩振动模的频率和相对强...     

A new type of phase transition in M(ClO4)2(H2O)6M = Fe,Co, Ni and Mn

Mössbauer studies on Fe(ClO₄)₂(H₂O)₆ salt showed anomalous quadrupole splitting around (230 ± 15)°K which we have established to be due to a new type of phase transition from pseudohexagonal to monoclinic system. Exactly similar type of transition was observed magnetically in all the isomorphous Ni²⁺, Co²⁺ and Mn²⁺ perchlorate hexahydrate single crystals at different critical temperatures.