The partial 1H NMR spectra of Al–OH and molecular H2O in hydrous aluminosilicate glasses: Component-Resolved analysis of 27Al–1H cross polarization and 1H spin-echo MAS NMR spectra

The Component-Resolved methodology was applied to ¹H spin-echo and ²⁷Al–¹H cross polarization (CP) MAS NMR data of aluminosilicate glasses. The method was able to resolve two components with different T2 relaxation rates, hydroxyl groups (OH) and molecular water (H₂O_mol), from the spin-echo data and to determine partial spectra and the relative abundances of OH and H₂O_mol. The algorithm resolved two to three components with different ²⁷Al–¹H CP dynamics from the ²⁷Al–¹H cross polarization data; the obtained partial NMR spectra for Al–OH are in excellent agreement with those obtained previously from the difference spectra between spectra with various contact times and confirm previous quantitative results and models for the Al–OH, Si–OH and H₂O_mol speciation (Malfait and Xue, 2010).     

高电荷态离子Arq+与不同金属靶作用产生的X射线

研究了高电荷态离子Ar^q+(q=16，17，18)入射金属Be，Al，Ni，Mo，Au靶表面产生的X射线谱.实验结果表明，Ar的Kα-X射线是离子在与固体表面相互作用过程中固体表面之下形成空心原子发射的.电子组态1s²的高电荷态Ar¹⁶⁺离子在金属表面中性化过程中，存在的多电子激发过程使Ar¹⁶⁺的K壳层电子激发产生空穴，级联退激发射Ar的Kα 特征X射线.Ar¹⁷⁺离子在金属表面作用过程中产生的X射线谱形与靶材料没有明显的关联,入射离子的Kα-X射线产额与其最初的电子组态有关，靶原子的X射线产额与入射离子的动能有关. 关键词： 高电荷态离子 空心原子 多电子激发 X射线     

Computational study of the surface properties of aluminum nanoparticles

We calculate the surface energy, surface stress, and lattice contraction of Al nanoparticles using ab initio density functional and empirical computational techniques. Ab initio calculations are carried out using the siesta pseudopotential method combined with the generalized gradient approximation. Empirical calculations are conducted using the embedded atom method. The ab initio density functional approach predicts the surface energies of Al nanoclusters to be in the range of 0.9-2.0 J/m². These values are consistent with the surface energy of bulk aluminum and are close to the surface energies of silver nanoparticles calculated in our previous study. In contrast to our previous results for Ag nanoparticles, we found a significant discrepancy between the theoretical values of surface energy and stress for Al nanoclusters. This result could be explained by a greater degree of surface reconstruction in Al clusters than in Ag clusters.     

Electronic structures of Al–Si clusters and the magic number structure Al8Si4

The low-energy structures of Al₈Si_m (m = 1–6) have been determined by using the genetic algorithm combined with density functional theory and the Second-order Moller-Plesset perturbation theory (MP2) models. The results show that the close-packed structures are preferable in energy for Al–Si clusters and in most cases there exist a few isomers with close energies. The valence molecular orbitals, the orbital level structures and the electron localisation function (ELF) consistently demonstrate that the electronic structures of Al–Si clusters can be described by the jellium model. Al₈Si₄ corresponds to a magic number structure with pronounced stability and large energy gap; the 40 valence electrons form closed 1S²1P⁶1D¹⁰2S²1F¹⁴2P⁶ shells. The ELF attractors also suggest weak covalent Si–Si, Si–Al and Al–Al bonding, and doping Si in aluminium clusters promotes the covalent interaction between Al atoms.     

Spectroscopic (FT‐IR,FT‐Raman,UV, 1H,and 13C NMR) and theoretical studies of m‐anisic acid and lithium,sodium, potassium,rubidium, and caesium m‐anisates

In order to understand the nature of the interactions of biologically important ligands, it is necessary to carry out the physico‐chemical studies of these compounds with their biological targets (e.g., receptors in the cell or important cell components). Results of this study make it possible to predict some properties of a molecule, such as its reactivity, durability of complex compounds, and kinship to enzymes. In this paper the effect of alkali metal cations (Li, Na, K, Rb, and Cs) on the electronic structure of m‐methoxybenzoic acid (m‐anisic acid) was studied. The experimental IR (in solid state and solution), Raman, UV (in solid state and solution), ¹H, and ¹³C NMR spectra of m‐methoxybenzoic acid, and its salts were registered, assigned, and analyzed. Some of the obtained results were compared with published data for o‐anisic acid and o‐anisates. The structures of anisic acid and Li, Na, and K m‐anisates were optimized at the B3LYP/6‐311++G** level. The IR, ¹H, and ¹³C NMR spectra and NPA, ChelpG, and MK atomic charges were calculated. The change of metal along with the series: Li → Na → K → Rb → Cs caused: (1) the change in the electronic charge distribution in anisate anion that is seen via the occurrence of the systematic shifts of several bands in the experimental and theoretical IR and Raman spectra of anisates; (2) systematic ¹H and ¹³C NMR chemical shifts; (3) hypsochromic shifts in UV spectra of salts as compared to ligands. Copyright © 2009 John Wiley & Sons, Ltd.     

27Al pulsed nuclear magnetic resonance study of CeAl2

The magnetic properties and the electronic structures of a rare-earth aluminum intermetallic compound CeAl₂ are investigated by magnetic susceptibility measurements and ²⁷Al pulsed nuclear magnetic resonance (NMR) techniques. The magnetic susceptibility is strongly temperature-dependent, following a Curie–Weiss law down to ∼12 K, and shows an antiferromagnetic transition at 4 K. The ²⁷Al NMR spectra show a typical powder pattern for a nuclear spin I of 5/2 with the second-order nuclear quadrupole interaction at high temperature and an additional large dipolar broadening between the 4f electron spins of cerium and the ²⁷Al nuclear spins at low temperature. The ²⁷Al NMR Knight shift follows the same temperature dependence as the magnetic susceptibility, suggesting that the ²⁷Al NMR Knight shift originates from the transferred hyperfine field of the Ce 4f electron spins with the hyperfine coupling constant of A = +5.7 kOe/μ_B. The spin-lattice relaxation rate 1/T₁ is roughly proportional to temperature, as with most non-magnetic metals at high temperature, and then strongly temperature-dependent, increasing rapidly with a peak near the antiferromagnetic transition temperature and decreasing at lower temperature. The temperature dependence of the Korringa ratio K, however, suggests that the antiferromagnetic spin fluctuation signature, which is an enhancement in the Korringa ratio, is washed out owing to the geometrical cancellation of Ce 4f fluctuations at the Al sites.     

Emission of X-ray continua by bombardment of thick Al,Si and Ti targets with protons and14N ions

Using thick targets the continuous X-ray spectra arising in the collision systems Al+p (0.5–7 MeV), Si+p (0.6–6 MeV), Si+¹⁴N (6 MeV, 14 MeV), Ti+p(1 MeV) and Ti+¹⁴N (14 MeV) were measured by means of a Si(Li) detector. Total yields were derived and compared with numerical results of calculations for secondary electron and nuclear bremsstrahlung. For Si and Ti the continuous spectra from one and the same target bombarded with protons and¹⁴N ions of equal velocity were investigated. Drastic deviations from theZ ₁ ² scaling have been found. They could be attributed to contributions of MO radiation originating by recoil of target atoms. The influence of characteristic line profiles on the measured spectra is also discussed.     

Evidences for strangelet presence in Primary Cosmic Rays

The recent results of experiment “Hadron” which was carried out at Tien-Shan Station in 1985–91 are discussed. The combining of extensive air shower array and large emulsion chamber has permitted to receive new experimental data on sharp scaling violation at energies ≥10¹⁵ eV (1 PeV). Data show strong hardness of hadron energy spectra in EAS cores for primary energies ≥3 PeV. The EAS electron lateral distribution function also exhibits the same energy dependence in interval 1–10 PeV. The EAS muon component also shows changing of energy dependence at 10 PeV. These data permit to discuss a model in which sharp scaling violation is connected with EAS spectrum “knee”. A hypothesis of strangelet presence in PCR is discussed. The flow of strangelet component is estimated to be about 1 m^?2 · year^?1.     

Influence of structural dynamics on charge recombination rates in photogenerated radical ion pairs: Evidence from EPR spectroscopy and computation

In order to better understand the dependence of charge recombination rate vs. temperaturek _CR(T) within a linear donor-chromophore-acceptor (D-C-A) molecular triad, the structural dynamics of the cation radical D⁺-C is studied individually using variable-temperature electron paramagnetic resonance (EPR) spectroscopy and electronic structure calculations. Here, the donor D isp-methoxyaniline, the chromophore C is 4-(N-piperidinyl)-naphthalene-1,8-dicarboximide, and the acceptor A is naphthalene-1,8∶4,5-bis(dicarboximide). The EPR spectra of D⁺-C exhibit marked changes in their overall shape throughout the 190–295 K temperature range. These spectra have hyperfine splittings that are strikingly well simulated with a model that includes methoxy group rotation, which occurs at a rate of 2.6 · 10⁴ s^?1 at 210 K and speeds up to 1.25 · 10⁷ s^?1 at 295 K, corresponding to an energy barrier of 38 kJ/mol. This considerable barrier reflects the partial conjugation between MeO and the aromatic ring and is confirmed by the calculated energy of a series of D^{+ ·}-C rotamers. The simulations also reveal that inversion of the anilino N center emerges atT > 250 K and can be represented by a planar and a pyramidal conformation with the equilibrium constantK = [pyramidal]/[planar] increasing from 0.029 at 250 K to 0.56 at 295 K. In the same temperature range, the charge recombination rate of D^{+ ·}-C-A^{? ·} accelerates abruptly and can be separated into two components, according to the above planar/pyramidal equilibrium. Thek _CR (T) of the pyramidal conformation has an activation energy of 41 kJ/mol, virtually the same as the barrier of MeO rotation. These results show that the intramolecular structural dynamics of the radical cation within D^+·-C-A^{? ·} control the overall charge recombination reaction with this radical ion pair.     

Collective flow model for the pion transverse momentum spectra from relativistic nuclear collisions at CERN

The transverse momentum spectra for pions observed by WA80 and NA35 collaborations are analysed within a fireball model with collective isentropic expansion and a realistic freeze-out criterion. By varing the initial state of the fireball, an excellent fit to the data is achieved for the whole measured range ofP _T . Slight differences in the data for the spectral slopes from central and pheripheral collisions originate in our model from the difference in the size of the fireball and in the number of participating nucleons in central and peripheral collisions. Using additional information from two-pion correlations, we can extrapolate our model back from the freeze-out point (determined from the spectra) to the initial state; we find that an initial energy density of 1.5–2GGeV/fm³ is sufficient to explain the data from central O+Au collisions at 200A GeV.     

Inflation of fireballs, the gluon wind and the homogeneity of the HBT radii at RHIC

We solve analytically the ellipsoidally expanding fireball hydrodynamics with source terms in the momentum and energy equations, using the non-relativistic approximation. We find that energy transport for high-p _tjets of gluons to the medium leads to a transient, exponential inflation of the fireballs created in high energy heavy ion collisions. In this transient, inflatory period, the slopes of the single particle spectra are exponentially increasing, while the HBT radius parameters are exponentially decreasing with time. This effect is shown to be similar to the development of the homogeneity of our Universe due to an inflatory period. Independently of the initial conditions, and the exact value of freeze-out time and temperature, the measurables (single particle spectra, the correlation functions, slope parameters, elliptic flow, HBT radii and cross terms) become time-independent during the late, non-inflatory stages of the expansion, and they satisfy a new kind of scaling laws. If the expansion starts with a transient inflation caused by the gluon wind, it leads naturally to large transverse flows as well as to the simultaneous equality, and scaling behaviour of the HBT radius parameters, R _side≈R _out≈R _long≈t _f √T _f /m. With certain relativistic corrections, the scaling limit is 281-2, where m _tis the mean transverse mass of the pair.     

Dy-doped Lu2SiO5 single crystal: spectroscopic characteristics and luminescence dynamics

Spectroscopic and kinetics properties of Lu₂SiO₅:Dy³⁺ (LSO:Dy) single crystal with 1 and 5 at.% of activator were investigated. The polarised absorption and unpolarised emission spectra were measured at 10–300 K. Parameters characterising radiative relaxations of LSO:Dy were estimated by the Judd–Ofelt model. The crystal-field energy structure was derived from low-temperature optical spectra exhibiting the presence of two non-equivalent Dy³⁺ sites. It was found that dysprosium ions in site 1 and in site 2 do not form isolated subsystems; these subsystems are coupled by an effective spectral energy migration process. The LSO:Dy crystal exhibits a strong luminescence in the visible. Strong ion–ion interactions were observed for LSO:Dy (5 at.%); luminescence decays are non-exponential and the macro-parameter of donor–acceptor interaction C _da amounts to 5.3 (10^?52 m⁶?s^?1) and 7.8 (10^?52 m⁶?s^?1) at 10 and 300 K, respectively. Laser potential related to the ⁴F_9/2→⁶H_13/2 yellow luminescence in Dy:LSO was assessed based on evaluation of the emission cross section values. It was concluded that the crystal is a promising material for visible laser operation.     

Hole polaron of small radius in assemblies of hydrated mono-protonated meso-tetraphenylporphine dimers at 77 K

Polaron theory is often used for the study of electrons and holes mobility in semiconductors when longitudinal optical (LO) phonons are generated upon the charge carriers moving. The polaron theory was applied to explain long-wavelength absorptions observed nearby Soret band in the electronic spectra of assemblies of mono-protonated meso-tetraphenylporphine dimer (TPP₂H⁺) that are interpreted as LO-phonons originated due to proton movement. The energy of hole polaron is found to be 1.50 eV at 77 K. Energy of Franck–Condon transitions of LO-phonons generated by hole polaron moving through water confined in the assemblies with distortions of O–H bonds is 0.2653 eV (2138 cm⁻¹). A broad band around 2127 cm⁻¹ corresponding the same energy of O–H bonds vibrations is observed in IR spectra of the assemblies consisting of water and mainly of TPP₂H⁺ species in the solid state indicating the presence of similar distortions of the hydrogen bonds. The radius of protonic sphere of 0.202 Å, which was estimated as a polaron quasiparticle moving through the confined water at 77 K, is found in agreement with earlier evaluated one of 0.265 Å that was obtained for proton diffusion at 298 K in similar assemblies.     

Electronic structure of PdO studied by photoemission (XPS,UPS)

In this paper we present the results of photoemission studies (XPS and UPS) performed on a polycrystalline surface of PdO. The electron density of states (EDOS) deduced both from XPS and UPS (He_I and He_II) are very similar. The valence band of PdO, which differs significantly from the Pd one, can be built up by four structures located at 0.5 eV, 2.2eV, 4.5 eV and 6.5 eV below E_F. The various electronic contributions (p or d) in the band are considered and, in order to explain our spectra, we discuss several hypothesis taking into account the possible existence of satellite lines or crystal field effects. Our XPS and UPS spectra show that the energy bands of PdO are narrow (～ 2–3 eV), moreover the energy shift of the core levels (|ΔE^F_B| = 2 eV) is important : these results suggest that the correlations between the d electrons may be important in PdO.     

Surface extended energy loss fine structures above the K-edge of oxygen on Al

Surface Extended Energy Loss Fine Structures (SEELFS) have been detected above the K-edge of oxygen adsorbed on an Al sample. This is the first evidence that the local geometry of adsorbates on metal surfaces can be investigated with the electron energy loss technique in the reflection mode. This experimental technique is highly surface sensitive and accurate bond lengths can be obtained. The oxidation model implied by our results for the OAl system is in agreement with data in the literature.     

Monte Carlo calculation of SU(2) glueball states with Symanzik's tree-level improved action

With the tree-level improved 4d SU(2) lattice gauge theory we carry out a Monte Carlo calculation of the spectrum. We find a scaling window for the 0⁺ state, leading to m(0⁺) ≈ 53 Λ^TI_L. Results for the 2⁺ state are somewhat inconclusive but also consistent with scaling.     

Kβ X-ray emission from He-like ions

Relativistic calculations on the energies and electric dipole rates of K_β X-rays from 1s3p(¹P₁,³P₁)-1s² (¹S₀) transitions for He-like ions in the range Z=14–54 are carried out using multi-configuration Dirac–Fock (MCDF) wave functions in the active space interaction approach. The contributions from Breit interaction and quantum electrodynamics have also been included in the calculation. An attempt has been made to find a scaling expression for Breit energy in terms of Zα .The scaled Breit energies are in good agreement with the earlier accurate relativistic results and this ensures the reliability of our scaling procedure. The behavior of MCDF wavefunctions for a given J in the non-relativistic limit has also been studied. The calculated K_β X-ray energies and rates agree well with other available experimental and theoretical values.     

Hadronic scaling and ratios of cosmic-ray components in the atmosphere

Using the scaling hypothesis of hadronic inclusive reactions at high energy and data from accelerators we compute ratios of cosmic-ray components in the atmosphere. For the μ⁺/μ^? ratio at sea level we find that the inclusion on nuclear effects results in a better agreement with experimental data. In the case of the (π⁺ + π^?)/p ratio, we predict a value at high energy that is considerably larger than the one usually inferred from lower energy data.     

Geometric scaling behavior of the scattering amplitude for DIS with nuclei

The main question, that we answer in this paper, is whether the initial condition can influence on the geometric scaling behavior of the amplitude for DIS at high energy. We re-write the non-linear Balitsky-Kovchegov equation in the form which is useful for treating the interaction with nuclei. Using the simplified BFKL kernel, we find the analytical solution to this equation with the initial condition given by the McLerran-Venugopalan formula. This solution does not show the geometric scaling behavior of the amplitude deeply in the saturation region. On the other hand, the BFKL Pomeron calculus with the initial condition at xA=1/mRA given by the solution to Balitsky-Kovchegov equation, leads to the geometric scaling behavior. The McLerran-Venugopalan formula is the natural initial condition for the Color Glass Condensate (CGC) approach. Therefore, our result gives a possibility to check experimentally which approach: CGC or BFKL Pomeron calculus, is more satisfactory.     

Electronic transitions of Ar,Xe, N2, CO physisorbed on Ag(111) and Al(111)

High Resolution Electron Energy Loss Spectroscopy has been extended to study also the excitonic (low lying electronic) transitions of physisorbed rare gas atoms (Ar, Xe) and diatomic molecules (N₂, CO) on Ag(111) and Al(111) surfaces at ～20K. Electron Loss Spectra were performed using a pair of hemispherical analyzers mounted at a fixed scattering angle (90°). This spectrometer allowed high transmission in the range of 0–15eV loss energies and incident beam energies up to 2OeV. AES, LEED and UV Photoemission (HeI) were also used in situ to characterize these surfaces and to identify the adsorbed gases and delineate their absolute coverage regimes.In contrast to optical absorption experiments, we observe both, optical (dipole) forbidden and allowed electronic transitions which show vibrational line structure for condensed multilayers. By comparison to gas phase data we find only weak perturbations in the condensed state. The observed electronic excitations show changes in intensity and FWHM depending on the coverage of the adsorbed gases.The FWHM of the electronic excitations of CO and N₂ adsorbed in the monolayer regime is larger than in multilayers. Nitrogen, on both surfaces exhibits an increase from 60meV to 120meV (FWHM) whereas for CO the vibronic features are broadened out leaving peaks with FWHM of ～1eV.The intensities of the electronic losses for all gases are smaller in the first monolayer than in the second or in multilayers. At submonolayer coverage the loss intensifies due to electronic excitations are strongly reduced and no longer observable although vibrational bands and photoelectron spectra show the presence of physisorbed adsorbates.Our results will be compared to optical absorption experiments (ref.1) on similar systems and to atom-on-jellium calculations (ref.2).