X-ray and UV photoelectron-spectroscopic studies of pyridine adsorbed on evaporated nickel and palladium in the temperature range 140–385 k

The states of pyridine adsorbed on evaporated nickel and palladium films have been investigated as a function of temperature in the range 140–385 K by means of X-ray and UV photoelectron spectroscopy. At ～ 140 K, pyridine “N-bonded” on the metal surfaces gives C 1s and N 1s peaks whose binding energies are very close to those for condensed pyridine and “N-bonded” pyridine on pre-oxidized nickel. The high-lying valence orbitals, 2b₁ (π) and 1a₂ (π) + 7a₁ (n), of pyridine show shifts similar to those for the “N-bonded” molecule on pre-oxidized nickel. At ～ 290 K, “π-bonded” pyridine shows large shifts in the C 1s and N 1s peaks and in the high-lying valence orbitals, as observed for “π-bonded” benzene on nickel. The assignments of the adsorbed states are supported by work-function change data. A large proportion of pyridine converts from the “N-bonded” to the “π-bonded” form between 220 and 290 K. Formation of “α-pyridyl” is suggested at ～ 375 K on nickel.     

Field emission and field ionization studies and their impact on the formulation of elementary steps in the heterogeneous activation of gas molecules by transition metal surfaces

The FIM and FEM evidence for the existence of the localized orbitals on transition metal surfaces and the problem of charge density distribution at the “stepped” surfaces (FEM and FIM tips) are reviewed. The role of these localized orbitals and of the nearly free electrons in the activation of gas molecules by transition metal surfaces is discussed.     

Photoelectron spectra of some fluorine substituted diazanaphthalenes

The high resolution He 584 Å photoelectron spectra of fluorine substituted 1,2-diaza-, 1,3-diaza-, 1,4-diaza- and 2,3-diaza-naphthalene are presented. By means of fluorine substitution the analysis of the photoelectron spectra of the parent compounds can be made more definite. Unexpected shifts of the nitrogen “lone-pair” bands can be explained within the through-space and through-bond interaction model. From this explanation one can deduce that fluorine substitution can give experimental evidence about the symmetry character of the “lone-pair” molecular orbitals.     

Strongly coupled bands as “effectively” decoupled bands

We present experimental evidence which suggests that almost all the strongly coupled bands in the rare-earth region may also be treated as “effectively” decoupled bands. In contrast to the usual decoupled bands, the strongly coupled bands seem to arise from a system where a particle carrying an “effective” angular momentumj′ is aligned to an even-even core having an “effective” rotational angular momentumR′ which is not necessarily zero for the band head but may even haveR′=2 or, 4 or, 6?etc. We attempt to explain these observations in a simple physical picture whereinJ _R, the projection ofj, the particle angular momentum, on the rotation axis, is taken as the effectively aligned spin of the last particle. Preliminary results from schematic bandmixing calculations forh _9/2 andf _5/2 orbitals with the Fermi energy lying near the highK single particle levels indeed reveal the existence of “effectively” decoupled bands which seem to agree with this physical picture.     

The UPS of some compounds containing the heteroatoms phosphorus,nitrogen, and oxygen

The “lone-pair” regions of the He(I) UPS of 25 compounds containing phosphorus, nitrogen, and oxygen as heteroatoms are presented and discussed. The semiempirical MNDO SCF MO method has been employed to compute the orbital energies of many of the molecules. Although this theoretical treatment seems to predict correct geometries and conformations for the molecules, it does not always reproduce the most logical orbital-ordering sequence. In particular, the phosphorus “lone-pair” orbitals tend to be computed too stable. The controversial interpretation of the UPS of tris-dimethylaminophosphine is reviewed.     

The electronic structures of the core and valence ion states of metal oxides

SCF-Xα SW MO calculations on metal core ion hole states and X-ray emission (XES) and X-ray photoelectron (XPS) transition states of the non- transition metal oxidic clusters MgO₆^10?, AlO₄^5? and SiO₄^4? show relative valence orbital energies to be virtually unaffected by the creation of valence orbital or metal core orbital holes. Accordingly, valence orbital energies derived from XPS and XES are directly comparable and may be correlated to generate empirical MO diagrams. In addition, charge relaxation about the metal core hole is small and valence orbital compositions are little changed in the core hole state. On the other hand, for the transition metal oxidic clusters FeO₆^10?, CrO₆^9? and TiO₆^8? relative valence orbital energies are sharply changed by a metal core orbital or crystal field orbital hole, the energy lowering of an orbital increasing with its degree of metal character. Consequently O 2p nonbonding → M 3d-O 2p antibonding (crystal field) energies are reduced, while M 3d bonding → O 2p nonbonding and M 3d-O 2p antibonding → M 4s,p-O 2p antibonding (conduction band) energies increase. Charge relaxation about the core hole is virtually complete in the transition metal oxides and substantial changes are observed in the composition of those valence orbitals with appreciable M 3d character. This change in composition is greater for e _g than for t_2g orbitals and increases as the separation of the e_g crystal field (CF) orbitals and the O 2p nonbonding orbital set decreases. Based on the hole state MO diagrams the higher energy XPS satellite in TiO₂ (at about 13 eV) is assigned to a valence → conduction band transition. The UV PES satellites at 8.2 eV in Cr₂O₃ and 9.3 eV in FeO are tentatively assigned to similar transitions to conduction band orbitals, although the closeness in energy of the crystal field and O 2p nonbonding orbitals in the valence orbital hole state prevents a definite assignment on energy criteria alone. However the calculations do clearly show that charge transfer transitions of the e_g bonding → e_g crystal field orbital type would generally occur at lower energy than is consistent with observed satellite structure.A core electron hole has little effect upon relative orbital energies and is only slightly neutralized by valence electron redistribution for MgO and SiO₂. For the transition metal oxides a core hole lowers the relative energies of M3d containing orbitals by large amounts, reducing O → M charge transfer and increasing M 3d crystal field → conduction band energies. Large and sometimes overcomplete neutralization of the core hole is observed, increasing from CrO₆^9? to FeO₆^10? to TiO₆^8?. as the O → M charge transfer energy declines.High energy XPS satellites in TiO₂ may be assigned to O 2p nonbonding → conduction band transitions while lower energy UV PES satellites in FeO and Cr₂O₃ arise from crystal field or O 2p nonbonding → conduction band excitations. Our “shake-up” assignment for FeO₆^10?, CrO₆^9? and TiO₆^8? are less than definitive because no procedure has yet been developed to calculate “shake-up” intensities resulting from transitions of the type described. However the results do allow a critical evaluation of earlier qualitative predictions of core and valence hole effects. First, we find that the comparison of hole or valence state ionic systems with equilibrium distance systems of higher nuclear and/or cation charge (e.g. the comparison of the FeO₆^10? Fe 2p core hole state to Co₃O₄) is dangerous. For example, larger MO distances in the ion states substantially reduce crystal field splittings. Second, core and CF orbital holes sharply reduce O → M charge transfer energies, giving 2e_g → 3e_g energy separations which are generally too small to match observed satellite energies. Third, highest occupied CF-conduction band energies are only about 4–5 eV in the ground states, but increase to about 7–11 eV in the core and valence hole states of the transition metal oxides studied. The energetic arguments presented thus support the idea of CF and/or O 2p nonbonding → conduction band excitations as assignments for “shake-up” satellites, at least in oxides of metals near the beginning of the transition series.     

分子空位缺陷对环三亚甲基三硝胺含能材料几何结构、电子结构及振动特性的影响

含能材料中的微观缺陷是导致“热点”形成并相继引发爆轰的重要因素. 然而, 由于目前人们对材料内部微观缺陷的认识不足, 限制了对含能材料中“热点”形成微观机理的理解, 进而阻碍了含能材料的发展和应用. 为了洞悉含能材料内部微观缺陷特性及探索缺陷引发“热点”的形成机理, 利用第一性原理方法研究了分子空位缺陷对环三亚甲基三硝胺(RDX) 含能材料的几何结构、电子结构及振动特性的影响, 探讨了微观缺陷对初始“热点”形成的基本机理. 采用周期性模型分析了分子空位缺陷对RDX几何结构、电子能带结构、电子态密度及前线分子轨道的影响. 采用团簇模型分析了分子空位缺陷对RDX振动特性的影响. 结果发现, 分子空位缺陷的存在使其附近的N–N键变长, 分子结构变得松弛; 使导带中很多简并的能级发生分离, 电子态密度减小, 并使由N-2p和O-2p轨道形成的导带底和价带顶均向费米面方向移动, 降低了能带隙值, 增加了体系活性. 前线分子轨道及红外振动光谱的计算分析表明, 分子缺陷使最高已占分子轨道电荷主要集中在缺陷附近的分子上, 且分子中C–H键和N–N键能减弱. 这些特性表明, 分子空位缺陷的存在使体系能带隙变小, 并使缺陷附近的分子结构松弛, 电荷分布增多, 反应活性增强; 在外界能量激发下, 缺陷附近分子将变得不稳定, 分子中的C–H键或N–N键较易先发生断裂, 发生化学反应释放能量, 进而成为形成“热点”的根源.     

Core-shell quantum dot electron bubbles as exotic ions in superfluid liquid 4He

A number of experiments in superfluid helium-4 over the past fifty years on the mobility of electron bubbles, which are unique quantum dots in the liquid state, revealed the existence of a “fast” ion and other “exotic” negative ions whose origin and structure still remains unresolved. The fast ion has a mobility which is six times that of the well understood single electron bubble and the other ions span a region from the fast ion mobility to that of the electron bubble. The work presented here shows that a net anionic, two electron, core-shell quantum dot could potentially explain these findings and provide direction for new experimental work. The model described is based on the quantum confinement and stabilization of short-lived shape resonances which originate from anti-bonding orbitals.     

Variational method for excited hartree-fock functionals

In this article variational approach is considered for determining excited Hartree-Fock orbitals. It is shown that for a model of an excited state of a system with “frozen” framework the variational method is equivalent to the method of potential V^N?1.     

Characterisation of some gold clusters by X-ray photoelectron spectroscopy

An XPS characterisation of the electronic structures of some polynuclear gold compounds is presented. The photoelectron spectra of the core levels and the valence bands are discussed in terms of the differing geometries and coordination environments in the metal clusters. The XPS analysis of “centred” and “non-centred” gold clusters shows characteristic features which operate a new distinction among these two classes of compounds.     

Electron momentum distributions and binding energies for the valence orbitals of hydrogen bromide and hydrogen iodide

Electron binding energy spectra and momentum distributions have been obtained for the valence orbitals of HBr and HI using noncoplanar symmetric electron coincidence spectroscopy at 1200 eV. The weakly bonding inner valence ns orbitals, which have not been observed previously, have their spectroscopic (pole) strength severely split among a number of ion states. For HBr the strength of the “main” inner valence (ns) transition is 0.42±0.03 whereas for HI it is 0.37±0.04, in close agreement with the value observed for the valence s orbitals of the corresponding isoelectronic inert-gas atoms. The spectroscopic strength for the two outermost orbitals is found to be close to unity, in agreement with many-body Green's function calculations. The measured momentum distributions are compared with several spherically averaged MO momentum distributions, as well as (for HBr) with a Green's function calculation of the generalized overlap amplitude (GOA). The GOA momentum distributions are in excellent agreement with the HBr data, both in shape and relative magnitude. Not all of the MO momentum distributions are in reasonable agreement with the data. Comparison is also made with the calculated momentum distributions for Kr, Br, Xe and I.     

Double-deck structure of the boundary layer in the problem of flow in an axially symmetric pipe with small irregularities on the wall for large Reynolds numbers

The problem of flow of a viscous incompressible fluid in an axially symmetric pipe with small irregularities on the wall is considered. An asymptotic solution of the problem with the double-deck structure of the boundary layer and the unperturbed flow in the environment (the “core flow”) is obtained. The results of flow numerical simulation in the thin and “thick” boundary layers are given.     

Nonlinear dynamics of breathers in the spiral structures of magnets

The structure and properties of pulsating solitons (breathers) in the spiral structures of magnets are analyzed within the sine-Gordon model. The breather core pulsations are shown to be accompanied by local shifts and oscillations of the spiral structure with the formation of “precursors” and “tails” in the moving soliton. The possibilities for the observation and excitation of breathers in the spiral structures of magnets and multiferroics are discussed.     

Electronic properties of alkali metal/silicon interfaces: A new picture

Adsorption of Na and Cs on the Si(100)2 × 1 surface in the monolayer range is investigated by core level and valence band photoemission spectroscopy using synchrotron radiation. The alkali metals are found to induce an electronic interface state near the Fermi level while hybridization between alkali adsorbate “s” and silicon substrate “3p” valence electrons occurs. These results provide evidence that the alkali metal/silicon bonding is covalent. This covalent bond is weak and polarized while plasmon at the alkali metal core level indicates adsorbate rather than substrate metallization.     

Hydrodynamic solutions of the generalized Boltzmann-Enskog equation

The properties of a kinetic equation are considered for systems of particles with a binary interaction containing a “hard core” and a far-range component. The solutions that correspond to periodic small perturbations of the distribution function are investigated.     

Preparation,characterization, and electrochemical performances of graphene/Ni(OH)2 hybrid nanomaterials

We report a class of core–shell nanomaterials that can be used as efficient surface-enhancement Raman scattering (SERS) substrates. The core consists of silver nanowires, prepared through a chemical reduction process, that are used to capture 4-mercaptobenzoic acid (4-MBA), a model analyte. The shell was prepared through a modified Stöber method and consists of patchy or full silica coats. The formation of silica coats was monitored via transmission electron microscopy, UV–visible spectroscopy, and phase-analysis light-scattering for measuring effective surface charge. Surprisingly, the patchy silica-coated silver nanowires are better SERS substrate than silver nanowires; nanomolar concentration of 4-MBA can be detected. In addition, “nano-matryoshka” configurations were used to quantitate/explore the effect of the electromagnetic field at the tips of the nanowire (“hot spots”) in the Raman scattering experiment.     

Topological bootstrap theory of hadrons

A topological framework is constructed for anS-matrix bootstrap theory of particles. Each component of anS-matrix topological expansion is associated with a pair of intersecting “quantum” and “classical” surfaces whose complexity exhibits an entropy property. The bounded classical surface embeds graphs that carry the direct observables — energymomentum, spin and electric charge. The closed quantum surface carries a triangulation whose orientations represent internal quantum numbers — which turn out to be baryon number, lepton number and flavor. A form of “color” automatically appears. All strong-interaction components of the expansion are generated through “Landau connected sums” from “zeroentropy” surface pairs — which are self generating. Elementary particles correspond to triangulated areas on the quantum surface; consistency at zero entropy determines allowed hadrondisks on quantum spheres together with the associated quantum numbers. Elementary topological hadrons turn out to include mesons, baryons and baryoniums, with quarks appearing as “peripheral triangles” (along the perimenters of hadron disks) whose attachments correspond to a total of 8 flavors as well as spin. Individual quarks do not carry momentum and cannot be hadrons; quark confinement is automatic. Also appearing within hadron disks are “core triangles” that carry baryon number and electric charge but no flavor or spin. Hadron disks have quantum numbers that accord with the lowestmass physically-observed mesons and baryons. The relation of topological theory to QCD is discussed.     

Self-trapping of electrons in vortex rings in liquid helium

A model according to which “fast” and “exotic” negative ions in superfluid helium are the localized states of electrons in vortex rings has been presented. The quantization of radial and longitudinal motions of electrons inside the vortex core and the quantization of the vortex motion of liquid helium lead to the existence of a whole family of excited states of electron vortices, in qualitative agreement with the experiments on the mobility of exotic ions. The possibility of the verification of conclusions of the model in optical experiments has been considered.     

Single-material coupling-tolerant semi-planar microresonator using Littrow diffraction

Resonators carved in a single material such as disc, rings, spheres, do not require genuine mirrors since they exploit shape resonances, but they then suffer from poor coupling to standard free-space collimated beams. Exploiting the idea of Littrow resonators combining total internal reflection and grating diffraction, we propose trapezoidal prism-type geometries that include a strong grating on one face, and total internal reflection on the other face. Resonant modes are localized within a length of the same order as the prism thickness, but are well coupled to free-space beams. The resonator core can be seen as a broad waveguide with multimode coupling of “Littrow modes”, a configuration recently pointed out for its capability to produce a “collective” slow-light regime. A more “planar” version, with a saw-tooth input-coupling grating for vertically collimated beam is also proposed.