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.     

CO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> radicals in synthetic hydroxyapatite

Powders of the B-type synthetic apatite exposed to gamma or ultraviolet irradiation were investigated using EPR spectroscopy. It was shown that ultraviolet irradiation leads to the appearance of the EPR spectrum near g = 2, which is similar to the spectrum observed upon gamma irradiation. The decomposition of the EPR spectra into components and the simulation of the shape of the experimental EPR signals revealed that these signals are associated primarily with two types of CO ₂ ^? radicals, namely, the axial CO ₂ ^? radicals and the orthorhombic CO ₂ ^? radicals. The differences in the shapes of the EPR spectra of the samples exposed to gamma and ultraviolet irradiation were explained by different ratios between the axial and orthorhombic CO ₂ ^? radicals. It was established that thermal annealing results in an increase in the relative contribution to the total EPR spectrum. This increase was explained by the transformation of the orthorhombic radicals into the axial radicals.     

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.     

F<Stack> <Subscript>3</Subscript> <Superscript>−</Superscript> </Stack> molecular ions in fluoride crystals

The UV absorption spectra of F₃^? molecular ions in LaF₃, SrF₂, CaF₂, and BaF₂ crystals doped with rare-earth elements are studied. Comparison of radiation-colored and additively colored crystals reveals the absorption bands of F₃^? hole centers in the region near 6 eV. Nonempirical calculations of optical transitions agree well with experimental results.     

Neutron-induced molecular defect O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> in beryllium orthogermanate

Be₂GeO₄ polycrystalline samples preliminarily irradiated by fast neutrons (E ～ 1 MeV, Φ = 4.5 × 10¹⁷ cm^?2) were studied by photoluminescence spectroscopy using synchrotron radiation pulses for excitation. The neutron-induced luminescence band observed at 1.7 eV in the spectra of the irradiated samples is assigned to the radiative relaxation of a molecular ion O ₂ ^? . The luminescence of these defects in the Be₂GeO₄ structure is effectively excited by 4.7-and 5.2-eV photons. At low temperatures (10 K), the profiles of the photoluminescence and excitation bands have a fine structure characteristic of electron-vibration interactions. The vibration frequencies for the ground state (v₁ = 161 cm^?1) and two excited states (v₂ = 672 cm^?1 and v₃ = 887?1451 cm^?1) were measured. Potential curves of the energy states of the O ₂ ^? center are constructed in terms of the Morse model using the experimental data. The optical spectrum fine structure is shown to be predominantly due to intrinsic vibrations of the molecular defect.     

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.     

High repetition rate LiF<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>: Color center laser

The efficient oscillation of LiF:F₂⁻ color center laser pumped by a compact LD-pumped Nd:YVO₄ acousto optically Q-switched laser with 30 kHz pulse repetition rate was demonstrated. The broadband oscillation with 75 μJ pulse energy and 37 kW peak power with the slope efficiency 20% was obtained. The average output power as high as 230 mW was reached. The narrow line tunable from 1.10 to 1.29 μm laser radiation with 10% conversion efficiency in the maximum of the tuning curve was achieved under pumping with 1.6 W average pump power.     

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.     

Magnetooptical properties of a molecular D<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>-ion in a quantum wire

In the framework of a model of zero-range potential, the problem of bound states of an electron in the field of two D0 centers (a two-center problem) in a semiconductor quantum wire is considered in the presence of a longitudinal magnetic field. It is shown that the magnetic field produces a significant shift of g and u terms and stabilizes the D ₂ ^? states in quantum wires. It is found that, in the case of transverse polarization of light, the spectral dependence of the photoionization cross section of a D ₂ ^? center exhibits the quantum-confined Zeeman effect with strongly pronounced oscillations of interference nature.     

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.     

A Simple and Neutral Receptor Acting as a Sensitive and Switch-on Fluorescent Chemosensor for H<Subscript>2</Subscript>PO<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack>

A novel artificial anion chemosensor 1 based on 2, 2′-di (4-nitrophenylurea-β-N-yl) -1, 1′-binaphthyl is designed and synthesized for sensing anions including halide ions and oxoanions. The fluorescent emission of the binaphthyl of receptor 1, forming the hydrogen bonding with anions as the sensing mechanism, is monitored in DMSO for detecting anions. In brief, while most of the anion chemosensors are switch-off fluorescent chemosensor, or non-fluorescent sensor, receptor 1 exhibits obviously the switch-on emission during the complexation with H₂PO₄⁻.     

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.     

Spectroscopy of the <Stack><Subscript>Λ</Subscript><Superscript>7</Superscript></Stack>He nucleus in a three-cluster model

The _Λ ⁷ He hypernucleus is considered within the _Λ ⁵ He + n + n cluster model. The hyperon—nucleon interaction is described by a one-boson-exchange potential that is constructed on the basis of the NSC97f model. Phenomenological potentials are used to describe the αΛ and αN interactions. For the _Λ ⁵ Hen interaction, use is made of the folding-model potential. The calculations of the hyperon binding energy in the ground state of the _Λ ⁷ He hypernucleus on the basis of Faddeev equations in configuration space yield a result (5.35 MeV) that agrees well with preliminary experimental data (5.4 MeV). The problem of calculating the hyperon binding energy within the three-body approach is discussed. In calculating the energy spectrum of _Λ ⁷ He, use is made of a version of the method of analytic continuation in the coupling constant. Low-lying excited states of this nucleus can be classified as an analog of the corresponding states of the ⁶He nucleus with allowance for the clustering of the _Λ ⁵ He+n+n system in the ⁶He(J ^π)+Λ(s) form.     

On the delay mechanism of Cl<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> diatomic anion dissociation up to the microsecond timescale

The dissociative capture of slow electrons by tetrachlorethylene (C₂Cl₄) has been investigated by resonant electron capture negative ion mass spectrometry. Metastable ions with fractional mass numbers 7.5, 17.5, and 19 corresponding to the C₂Cl₄⁻ → Cl⁻ + C₂Cl₃ and Cl₂⁻ → Cl⁻ + Cl decays occurring at the microsecond timescale have been detected. It has been revealed that Cl₂⁻ anions, which are fragment ions, can dissociate at the microsecond timescale, which is very surprising for a system with one internal degree of freedom. This process is assumingly attributed to the rotational excitation of Cl₂⁻ anions. Thus, the experimental estimate of the time of rovibronic relaxation in the Cl₂⁻ anion has been obtained.     

Laser control of low-temperature reaction <Emphasis Type="Italic">e</Emphasis><Superscript>−</Superscript> + O<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack>

A theory is developed to describe dissociative recombination of a slow electron with a ground-state molecular ion of oxygen driven by a strong monochromatic electromagnetic field. Mathematically, the theory is based on the time-independent formalism of radiative scattering matrix whose poles correspond to dressed intermediate states of the complex. The analysis embraces both transitions to dissociative states and laserinduced nonadiabatic transitions to intermediate bound states of valence configurations. Key reaction mechanisms are considered, and a classification is given of all allowed transitions to dissociative states. Partial and total reaction cross sections are calculated by taking into account the contributions from Rydberg, valence, and dissociative states of O₂^**. A detailed discussion of results is presented, and feasibility of laser control of the reaction is demonstrated.     

Optimized semiempirical potential energy surface for H<Subscript>2</Subscript><Superscript>16</Superscript>O up to 26000 cm<Superscript>−1</Superscript>

A semiempirical potential energy surface is obtained for the major isotopologue of the water molecule H₂ ¹⁶O that allows the vibration-rotation energy levels in the range of 0–26000 cm⁻¹ to be calculated with an accuracy almost equal to the average experimental accuracy of measurements in the infrared and visible ranges. Variational calculations using this potential energy surface reproduce the experimental energy values of more than 1500 vibration-rotation levels of H₂ ¹⁶O with the total angular momentum quantum number J = 0, 2, and 5 in the indicated range with a standard deviation of 0.022 cm⁻¹. The potential was obtained by optimizing a starting ab initio surface using a combination of two approaches, i.e., (1) the multiplication of the starting ab initio surface by a morphing function whose parameters were optimized and (2) the optimization of parameters of the ab initio surface using both the experimental values of energy levels and the results of quantum-chemical electronic structure calculations.     

Laser control of the low-temperature <Emphasis Type="Italic">e</Emphasis><Superscript>−</Superscript>+O<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> reaction

The dissociative recombination theory of slow electrons with molecular ions in a strong monochromatic light field is developed. Classifications of all possible transitions and reaction mechanisms are presented. The potential energy curves of the oxygen molecule O₂^** dissociative states and partial cross sections are calculated.     

<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.     

<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.