O<Subscript>2</Subscript> photodesorption from AuO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and Au<Subscript>2</Subscript>O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>

Using time-resolved photoelectron spectroscopy, the decay channels of AuO₂⁻ and Au₂O₂⁻ following photoexcitation with 3.1-eV photons have been studied. For AuO₂⁻, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption can be excluded. For Au₂O₂⁻, the spectra indicate O₂ desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au _n O₂⁻ with analogous data on Ag _n O₂⁻ clusters, a discernible pattern emerges: for dissociatively bound O₂(AuO₂⁻, Ag₃O₂⁻), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au₂O₂⁻, Ag₂O₂⁻, Ag₄O₂⁻, Ag₈O₂⁻), the 3.1-eV photoexcitation triggers fast O₂ desorption with a high quantum yield.     

Potential energy of <Superscript>∞</Superscript>H<Stack><Subscript>2</Subscript><Superscript>-</Superscript></Stack>(<Superscript>2</Superscript>∑<Stack><Subscript>u</Subscript><Superscript>+</Superscript></Stack> in the bound-state region

An accurate calculation of the lowest negative electronic state of H ₂ ^- (fixed nuclei) is reported using the CCSD(T) method and doubly augmented cc-pv5z basis set. Comparison has been made with the reference data by Senekowitsch et al. [Chem. Phys. Lett. 111 (1984) 211]. Owing to larger size of the basisset and inclusion of triple excitations, no vertical shift in this work is necessary to reproduce the asymptotics of H + H ^-. In addition, the effect of basis-set truncation is estimated, based on the complete-basis-set extrapolation method. The contribution of correlated electron-proton motion to the electron-energy curve for H₂ ^– dynamics is pointed out.Dedicated to Prof. Jií Horáek on the occasion of his 60th birthday.     

Odd autoionizing 2p<Subscript>1/2</Subscript><Superscript>5</Superscript>n(s<Superscript>′</Superscript>/d<Superscript>′</Superscript>) resonances of Ne excited from the 2p<Superscript>5</Superscript>3p[K]<Subscript>J</Subscript> states

Absolute photoionization cross sections for Ne atoms in the excited levels (Paschen notation ) were calculated at near threshold energies within the configuration interaction Pauli-Fock approach including core polarization. The computed spectra and the lineshape parameters of the odd parity 2p_1/2 ⁵ns^′/d^′ autoionizing resonances are found to be in good agreement with high resolution laser spectroscopic results. Guided by the theoretical results, improved analyses of the measured spectra by superimposed Fano-type profiles were achieved. Theoretical predictions are presented for resonances which have not yet been studied experimentally. In addition, we report the absolute partial photoionization cross sections for the ²P_3/2 and ²P_1/2 channel at photoelectron energies up to 7 eV. Except for the highest lying 2p₁(¹S₀) level, these cross sections monotonically decrease with energy (as reported earlier in single-electron calculations for the Ne(2p⁵3p) configuration) with branching ratios which essentially reflect the core composition of the 2p_x levels. For the 2p₁ level the resonance structure and the partial cross sections are strongly influenced by a Cooper-Seaton minimum in the d_3/2 ^′ channel,located just above the ²P_1/2 ionization limit.     

On the energy of the 8<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> 1479-keV level in <Superscript>178</Superscript>Hf

The difference in the 332-and 326-keV transition energies from ¹⁷⁸Ta decay is measured with a magnetic β spectrometer and a γ spectrometer. The energy of the 332-keV transition (E(332) = 331 607 ± 4 eV) and the energy of the 8 ₂ ^? 1479-keV level in ¹⁷⁸Hf (E(1479) = 1479001 ± 6 eV) are determined with high accuracy.     

EIT Ground State Cooling Scheme of <Superscript>171</Superscript>Yb<Superscript>+</Superscript> Based on the <Superscript>2</Superscript>S<Subscript>1/2</Subscript>→<Superscript>2</Superscript>P<Subscript>1/2</Subscript> Cooling Transition

We propose a method for EIT ground state cooling of ¹⁷¹Yb+ ion, which involves three light fields with detuning on a MHz scale. The steady-state mean vibrational quantum number is calculated to be less than 0.005. Efficient cooling is achievable in a motional-mode frequency range of 2π · (1.5 ± 0.5 MHz).     

Analysis of the vector form factors f<Superscript>+</Superscript><Subscript>Kπ</Subscript>(Q<Superscript>2</Superscript>) and f<Superscript>-</Superscript><Subscript>Kπ</Subscript>(Q<Superscript>2</Superscript>) with light-cone QCD sum rules

In this article, we calculate the vector form factors f⁺ _Kπ(Q²) and f^- _Kπ(Q²) within the framework of the light-cone QCD sum rule approach. The numerical values of f⁺ _Kπ(Q²) are compatible with existing theoretical calculations, and the central value of f⁺ _Kπ(0) (f⁺ _Kπ(0)=0.97) is in excellent agreement with the values from chiral perturbation theory and lattice QCD. The values of |f^- _Kπ(0)| are very large compared to the theoretical calculations and experimental data, and they cannot give any reliable prediction. At large momentum transfer with Q² > 5 GeV², the form factors f⁺ _Kπ(Q²) and |f^- _Kπ(Q²)| can either show the asymptotic behavior of or decrease more quickly than ; more experimental data are needed to select the ideal sum rules. PACS 12.38.Lg; 12.38.Bx; 12.15.Hh     

Hyperfine Interactions in Pb<Superscript>3+</Superscript>F<Stack><Subscript>8</Subscript><Superscript>−</Superscript></Stack>F<Stack><Subscript>a</Subscript><Superscript>−</Superscript></Stack> clusters in fluorite crystals

The parameters of hyperfine interactions in Pb³⁺F ₈ ^? F _a ^? tetragonal clusters of MeF₂ crystals (Me=Ca, Sr, Ba) are interpreted. The contributions of the spin polarization to the parameters of the proper hyperfine interaction and additional (ligand) hyperfine interactions are calculated in the approximation of weak binding between a charge-compensating ion F _a ^? and a cubic fragment in the tetragonal cluster. It is demonstrated that correct inclusion of the contributions from the spin polarization to the ligand isotropic hyperfine interaction for the F _a ^? ion leads to anomalously large parameters of this interaction for MeF₂ crystals. These results are in agreement with experimental data.     

On the origin of <Emphasis Type="Italic">E</Emphasis><Subscript>0</Subscript> ≥ 10<Superscript>17</Superscript> eV cosmic rays according to data from the Yakutsk array for studying extensive air showers

Results are presented that were obtained by analyzing the energy spectrum and anisotropy of E ₀ ≥ 10¹⁷ eV primary cosmic rays on the basis of data accumulated at the Yakutsk array for studying extensive air showers over the period between 1974 and 2004. It is shown that spectra corresponding to different regions of the sky differ in shape. Particle fluxes going from the Galaxy and Supergalaxy (a local supercluster of galaxies) disks are enhanced for E ₀ ≥ 5 × 10¹⁸ eV and are reduced for E ₀ ≤ (2–3) × 10¹⁸ eV. This observation is interpreted as a manifestation of the possible interaction between extragalactic primary cosmic rays and matter of the above structures of space.     

<Superscript>2</Superscript>H NMR investigation of the transition to the proton glass state in the Cs<Subscript>5</Subscript>H<Subscript>3</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript> · 0.5H<Subscript>2</Subscript>O crystal

A crystal of the Cs₅H₃(SO₄)₄ · xH₂O (x ≈ 0.5) (PCHS) compound, which belongs to the family of proton conductors with a complex system of hydrogen bonds, is investigated by ²H NMR spectroscopy. The temperature and orientation dependences of the ²H NMR spectra are measured and analyzed. It is established that, upon transition to the glassy phase at the temperature T _g = 260 K, the parameters characterizing the proton exchange between positions in hydrogen bonds remain unchanged to within the limits of experimental error. The protons in the two-dimensional network of hydrogen bonds in the (001) plane are dynamically disordered over possible positions down to temperatures considerably lower than the glass transition point T _g . However, water molecules are fixed at particular structural positions in the phase transition range. In PCHS crystals with a nonstoichiometric water content, this circumstance can be responsible for the frustration that leads to the formation of the glassy state.     

Ordered structure of the directions of arrival of E<Subscript>0</Subscript>∼5×10<Superscript>17</Superscript> eV cosmic rays according to data from the Yakutsk array for recording extensive air showers

Results are presented that were obtained by analyzing arrival directions for cosmic rays recorded by the Yakutsk array between 1974 and 2001 in the energy range E₀=10^17.6–17.9 eV for zenith angles in the region θ≤53°. It is shown that their flux consists of two components—an isotropic (about 75%) and a cluster (about 25%) one—that are characterized by sharply different degrees of anisotropy. At E₀=10^17.7–17.8 eV, the observed showers are found to be strongly correlated with the Supergalaxy plane.     

Origin of the structural local transition in the molecular impurity ion MnO<Stack><Subscript>4</Subscript><Superscript>2−</Superscript></Stack> in the K<Subscript>3</Subscript>Na(CrO<Subscript>4</Subscript>)<Subscript>2</Subscript> ferroelastic

A new model is proposed for a local transition in a Jahn-Teller impurity center in a crystal with a ferroelastic (ferroelectric) phase transition. This model is based on direct interaction of the order parameter of the phase transition in the matrix with the Jahn-Teller impurity degrees of freedom. It is shown that, under these conditions, the order parameter field can induce lifting of degeneracy of the electronic states active in the Jahn-Teller effect, which is accompanied by a transition from the Jahn-Teller effect to the pseudo-Jahn-Teller effect with its subsequent suppression. As a result, a decrease in temperature gives rise to a structural local transition in the region of the low-symmetry ferroelastic (ferroelectric) matrix phase from the many-well local adiabatic to a single-well potential. The model proposed allows interpretation of experimental data obtained in an EPR study of the molecular impurity ion MnO ₄ ^2? in the K₃Na(CrO₄)₂ ferroelastic.     

Small-scale anisotropy and composition of <Emphasis Type="Italic">E</Emphasis><Subscript>0</Subscript> ≈ 10<Superscript>17</Superscript> eV cosmic rays according to data from the Yakutsk array for studying extensive air showers

Results are presented that were obtained from an analysis of arrival directions for cosmic rays of energy in the range E ₀ ≈ 10^16.9–17.2 eV that were recorded by the Yakutsk array between 1974 and 2001 at zenith angles of θ ≤ 45°. It is shown that a considerable part of them form clusters that have small-scale cellular structure. In all probability, these showers are generated by neutral particles of an extragalactic origin.     

<Superscript>57</Superscript>Fe emission Mössbauer spectroscopy following dilute implantation of <Superscript>57</Superscript>Mn into In <Subscript>2</Subscript>O<Subscript>3</Subscript>

Emission Mössbauer spectroscopy has been utilised to characterize dilute ⁵⁷Fe impurities in In ₂O₃ following implantation of ⁵⁷Mn (T _1/2 = 1.5 min.) at the ISOLDE facility at CERN. From stoichiometry considerations, one would expect Fe to adopt the valence state 3 + , substituting In ³⁺, however the spectra are dominated by spectral lines due to paramagnetic Fe²⁺. Using first principle calculations in the framework of density functional theory (DFT), the density of states of dilute Fe and the hyperfine parameters have been determined. The hybridization between the 3d-band of Fe and the 2p band of oxygen induces a spin-polarized hole on the O site close to the Fe site, which is found to be the cause of the Fe²⁺ state in In ₂O₃. Comparison of experimental data to calculated hyperfine parameters suggests that Fe predominantly enters the 8b site rather than the 24d site of the cation site in the Bixbyite structure of In ₂O₃. A gradual transition from an amorphous to a crystalline state is observed with increasing implantation/annealing temperature.     

The effect of the halide-ion (F<Superscript>–</Superscript>, Cl<Superscript>–</Superscript>) dopant nature on the local structure and hydration processes of brownmillerite Ba<Subscript>2</Subscript>In<Subscript>2</Subscript>O<Subscript>5</Subscript>

Halogen-substituted barium indate Ba₂In₂O₅ based brownmillerites Ba_1.95In₂O_4.9F_0.1 and Ba_1.95In₂O_4.9Cl_0.1 have been synthesized. It has been verified radiographically that the single-phase condition is satisfied. The effect of the substituent ion nature on parameters of the crystalline lattice and lengths of In–O bonds has been revealed. The propensity of the phases under study for hydration and formation of energetically unequal ОН^– groups in the structure has been proved. In both the cases of doping, the degree of hydration decreased as compared to barium indate Ba₂In₂O₅, which is caused by the participation of the halide ion in the tetrahedral site of indium.     

On the formation of protected gold nanoparticles from AuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> by the reduction using aromatic amines

Amines are used extensively as reductants and subsequent capping agents in the synthesis of metal nanoparticles, especially gold, due to its affinity to nitrogen. Taking 2-methyl aniline as an example, we show that metal reduction is followed by polymerization of the amine, while part of it covers the nanoparticle surface another fraction deposits in the solution. It is found that the oxidative polymerization of the amine goes in step with the formation of gold nanoparticles. The gold nanoparticles thus formed have a mean diameter of 20 nm. The polymerized amine encapsulates the gold nanoparticle forming a robust shell of about 5 nm thickness, making the gold core inert towards mineralizing agents such as chloroform, bromoform, sodium cyanide, benzylchloride, etc. which react with the naked gold nanoparticles. The deposited polymer is largely protonated, taking up protons from the medium during its formation. Similar results have been observed in the case of aniline also. The materials have been fully characterized by spectroscopy and microscopy.This revised version was published online in August 2005 with a corrected issue number.     

Short-range magnetic order in LaMn(O<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>F<Subscript>x</Subscript>)<Subscript>3</Subscript> from <Superscript>139</Superscript>La and <Superscript>19</Superscript>F NMR data

The temperature behavior of the ¹³⁹La and ¹⁹F NMR spectra was studied for polycrystalline LaMn(O_1?xF_x)₃ with a partial substitution of fluorine for oxygen. The temperature dependences of the ¹³⁹La and ¹⁹F NMR line shapes were found to be substantially different. An appreciable broadening of the ¹⁹F NMR spectrum and a fixed position of line maximum with lowering temperature is indicative of the presence of a short-range magnetic order in the paramagnetic temperature region (T>T _N ).     

<Superscript>151</Superscript>Eu Mössbauer study of multiferroic Eu<Subscript>0.75</Subscript>Y<Subscript>0.25</Subscript>MnO<Subscript>3</Subscript>

We are herewith reporting the ¹⁵¹Eu Mössbauer spectra collected on a polycrystalline powder sample of Eu_0.75Y_0.25MnO₃ from 15 K to room temperature. All the spectra consist of a single line, whose shape and related sample thickness are dependent on the temperature T. The thermal trend of the mean square displacement of Eu ion, obtained from the spectra analysis, clearly reveals a large low-temperature anharmonicity and in concomitance with the onset of the magnetic ordering consists in a linear strong decrease interrupted by two narrow wells at 29.5 K and 40 K. This behavior is interpreted in connection with the transfer of spectral weight from the 120 cm^-1 optical phonon to the electromagnonic modes. The T-trend of the central shift shows that Eu³⁺ electronic ground state in the magnetically ordered phase differs from the one in the paramagnetic state. Finally, the temperature dependence of the hyperfine field under T _N gives a contribution to interpret some controversial features regarding the phase-diagram.     

<Superscript>10</Superscript>B–<Superscript>11</Superscript>B isotope substitution and superconductivity in ZrB<Subscript>12</Subscript>

The specific heat of the ZrB₁₂ compound in the normal and superconducting states (T _C ≈ 6 K) has been studied in the 1.9–7 K temperature range for high-quality single crystals with different relative contents of boron isotopes. For Zr¹⁰B₁₂, Zr^natB₁₂, and Zr¹¹B₁₂ dodecaborides, the electron density of states and the electronphonon coupling constant, λ_e-ph ∼ 0.4, are found. The dependence of the thermodynamic and upper critical fields, as well as of the Ginzburg-Landau parameter (κ = 0.8–1.14) on temperature and isotope composition is determined. The results suggest the existence of the magnetic field induced phase transition at T* = 4–5 K, which is not related to the transition from type-I to type-II superconductivity. The possibilities of the existence of two-gap superconductivity and a structural phase transition at T* in zirconium dodecaboride are discussed.