Chromium tracer diffusion in NiO crystals

Diffusion of ⁵¹Cr in NiO single crystals in air has been studied by the tracer-sectioning technique. In the temperature range 1192–1642°C, the diffusion coefficient can be expressed by the Arrhenius expression D=D_oexp(-Q/RT), with D_o=(8·6±1·2)×10^?3 cm²/sec and Q=67·4±1·1 kcal/mole. The use of a high specific-activity tracer and a special configuration for the diffusion anneal prevented the self-dopling effect found by Seltzer and the evaporation of chromium from the sample surface. The present results, in conjunction with published results on nickel self-diffusion in NiO and interdiffusion in the NiO?Cr₂O₃ system, are used to determine a chromium ion-vacancy binding energy of about 5 kcal/mole in pure NiO.     

Study of the OZI selection rule in hadronic processes

In the experiments with LEPTON-F and SPHINX spectrometers the pion-induced charged exchange reactions π- + p → ? + n and π- + p → ω + n at Pπ-=32.5 GeV, as well as proton-induced diffractive reactions p + N → [p?] + N and p + N → [pω] + N at E _p =70 GeV were studied. The comparison of the cross-sections for ? and ω-production in these reactions is used for testing the OZI selection rule in hadronic processes. It has been demonstrated that in pion reactions the ratio of the yields of ? and ω-mesons R(?/ω) = (3 ± 1) · 10^?3 is in a good agreement with naive quark model prediction based on the mixing in vector meson nonet and on the OZI rule (R(?/ω)ozi = tg ²Δθ _V ? 4 · 10^?3). At the same time in proton reactions the effective ratio of ? and ω yields is ～ (4 ÷ 7) · 10^-2, i.e. a strong violation of the OZI rule is observed in proton-nucleon interactions. This violation can be in favor of possible existence of some exotic ss? component in the quark structure of protons.     

Application of semiclassical collision theory to the collinear reactive H+H2 system

Semiclassical collision theory using the stationary-phase method and the near classical method was applied to the collinear H+H₂ system, in the (total) energy range E = 12·5-30 kcal/mole. It was found that although the near classical method was applicable in the near-threshold energy range of E = 13-17 kcal/mole, and both methods gave qualitatively correct results for E > 17 kcal/mole, yet there was no good quantitative agreement with the exact results.     

Hydrogen bonding and aromaticity in the guanine–cytosine base pair interacting with metal cations (M = Cu+, Ca2+ and Cu2+)

The influence of metal cations (M?=?Cu⁺, Ca²⁺ and Cu²⁺) coordinated to the N₇ of guanine on hydrogen bonding and aromaticity of the guanine–cytosine base pair has been analysed with the help of delocalization indices using the B3LYP functional. Our analysis shows that the strengthening of the N₁···N₃ and N₂···O₂ hydrogen bonds and the weakening of the O₆···N₄ hydrogen bond is mainly caused by the modification of donor–acceptor (covalent) interactions rather than to a significant change of electrostatic interactions. On the other hand, the increase of the aromaticity of the guanine and cytosine six-membered rings because of the interaction with Cu⁺ and Ca²⁺ is attributed to the strengthening of hydrogen bonding in the guanine–cytosine pair. The observed reduction of aromaticity in the five- and six-membered rings of guanine due to ionization or interaction with Cu²⁺ is caused by the oxidation process that removes a?π?electron disrupting the?π?electron distribution.     

Spectrum and energy levels of Cr3+ ions and exchange-coupled Cr3+ pairs in lanthanum aluminate

From the optical spectra the energy levels of the Cr³⁺ ion in LaAlO₃ were determined. In the cubic field approximation we obtained with the parametersDq=1750cm^-1,B=661 cm^-1, andC=2908 cm^-1 a good agreement between the calculated and measured energies. For higher Cr³⁺ concentrations the fluorescence spectrum of the exchange-coupled first nearest (1N) Cr³⁺ pairs was separated from the vibronic fluorescence spectrum of the single ions by selective excitation. From the experimental data the energy level scheme of the 1N pairs is constructed for the states ¦⁴ A ₂·⁴ A ₂〉 and ¦⁴ A ₂·² E〉. In the ground state the pairs are ordered antiferromagnetically due to an isotropic exchange interaction with an exchange integralJ=(?68 ± 1) cm^-1. From the fluorescence decay the intrinsic lifetimes of the fluorescent states of the single ions, the 1N and the 2N pairs were determined to be equal to (86± 4) msec, (1.75± 0.25) msec, and (31 ± 5) msec respectively. The fluorescence decay shows an energy transfer between the single ions and the pairs.     

Absolute cross sections of electron attachment to molecular clusters. Part II: Formation of (H2O) N? , (N2O) N? , and (N2) N?

Absolute cross sections σ⁻(E, N) of electron attachment to clusters (H₂O) _N , (N₂O) _N , and (N₂) _N for varying electron energy E and cluster size N are measured by using crossed electron and cluster beams in a vacuum. Continua of σ⁻(E) are found that correlate well with the functions of electron impact excitation of molecules’ internal degrees of freedom. The electron is attached through its solvation in a cluster. In the formation of (H₂O) _N ⁻ , (N₂O) _N ⁻ , and (N₂) _N ⁻ , the curves σ⁻(N) have a well-defined threshold because of a rise in the electron thermalization and solvation probability with N. For (H₂O)₉₀₀, (N₂O)₃₅₀, and (N₂)₂₆₀ clusters at E = 0.2 eV, the energy losses by the slow electron in the cluster are estimated as 3.0 × 10⁷, 2.7 × 10⁷, and 6.0 × 10⁵ eV/m, respectively. It is found that the growth of σ⁻ with N is the fastest for (H₂O) _N and (N₂) _N clusters at E → 0 as a result of polarization capture of the s-electron. Specifically, at E = 0.1 eV and N = 260, σ⁻ = 3.0 × 10⁻¹³ cm² for H₂O clusters, 8.0 × 10⁻¹⁴ cm² for N₂O clusters, and 1.4 × 10⁻¹⁵ cm² for N₂ clusters; at E = 11 eV, σ⁻ = 9.0 × 10⁻¹⁶ cm² for (H₂O)₂₀₀ clusters, 2.4 × 10⁻¹⁴ cm² for (N₂O)₃₅₀ clusters, and 5.0 × 10⁻¹⁷ cm² for (N₂)₂₆₀ clusters; finally, at E = 30 eV, σ⁻ = 3.6 × 10⁻¹⁷ cm² for (N₂O)₁₀ clusters and 3.0 × 10⁻¹⁷ cm² for (N₂)₁₂₅ clusters. Original Russian Text ? A.A. Vostrikov, D.Yu. Dubov, 2006, published in Zhurnal Tekhnicheskoĭ Fiziki, 2006, Vol. 76, No. 12, pp. 1–15.     

Effect of 50 MeV Li+3 and 80 MeV C+5 ions’ beam irradiation on the optical,structural, chemical and surface topographic properties of PMMA films*

The self-standing films of polymethyl methacrylate (PMMA) were irradiated under vacuum with 50?MeV lithium (Li³⁺) and 80?MeV carbon (C⁵⁺) ions to the fluences of 3?×?10¹⁴, 1?×?10¹⁵, 1?×?10¹⁶ and 1?×?10¹⁷ ions µm^?2. The pristine and irradiated samples of PMMA films were studied by using ultraviolet–visible (UV–Vis) spectrophotometry, Fourier transform infrared, X-ray diffractrometer and atomic force microscopy. With increasing ion fluence of swift heavy ion (SHI), PMMA suffers degradation, UV–Vis spectra show a shift in the absorption band from the UV towards visible, attributing the formation of the modified system of bonds. E_g and E_a decrease with increasing ion fluence. The size of crystallite and crystallinity percentage decreases with increasing ion fluence. With SHI irradiation, the intensity of IR bands and characteristic bands of different functional groups are found to shift drastically. The change in (E_g) and (N) in carbon cluster is calculated. Shifting of the absorption band from the UV towards visible along with optical activity and as a result of irradiation, some defects are created in the polymer causing the formation of conjugated bonds and carbon clusters in the polymer, which in turn lead to the modification in optical properties that could be useful in the fabrication of optoelectronic devices, gas sensing, electromagnetic shielding and drug delivery.     

An N.M.R. study of molecular motion in solid trimethylaminegallane

Continuous wave and pulsed ¹H N.M.R. data have been obtained for solid H₃GaN(CH₃)₃ over the temperature range 63–300 K. A theoretical expression for the relaxation behaviour of a methyl group in a trimethylamine moeity undergoing various motions has been obtained to aid analysis of the data. We find the activation energy to rotation of the -GaH₃ group to be 3·6 ± 0·3 kJ/mole (0·86 ± 0·07 kcal/mole), and to a different motion in the molecule to be 21 ± 2 kJ/mole (5·0 ± 0·5 kcal/mole). In the continuous wave spectra effects due to motion of the -CH₃ groups and the whole -NMe₃ moeity may be distinguished.     

Quantum chemical studies of the solvation of the hydroxide ion

Abstract

To understand and model the solvation of the hydroxide ion, OH(H₂O)^? _n clusters, n = 1?5, are studied using ab initio quantum chemical techniques, largely at the MP2 level of theory using a double zeta plus polarization functions basis extended by diffuse functions. Energies and vibrational frequencies, together with thermodynamic quantities such as enthalpies, entropies and Gibbs free energies, are computed. This permits comparison with experimental estimates of the successive thermodynamic changes associated with the reaction OH(H₂O)^? _n + H₂O → OH(H₂O)^? _n+1. The theoretical values are in good agreement with experiment. The free energy of hydration of OH^? is modelled by a composite discrete-continuum method where the effects of the first hydration shell (n = 3) are obtained from the gas phase cluster calculation, while the long-range effects are modelled using self consistent reaction field theory, namely by calculating the solvation energy of OH(H₂O)^? _n in a dielectric continuum. The best estimate of the solvation (free) energy at 298 K is ?84·5 kcal mol^?1, compared to the experimental value of ?102·8 kcal mol^?1.     

Mößbauereffekt in Eisenstilben und FeCl2·H2O

Using Mößbauer effect measurements in the temperature range between 3 °K and 310 °K the magnetic fields at the nucleus in iron-stilbene, FeCl₂·H₂O and FeCl₃ are determined to beH _T=0=(250±10) kOe, (252±18) kOe and (468±10) kOe; a Néel-temperature ofT _N=(23±1) °K is measured for iron-stilbene. The electric quadrupole splittings atT=0 °K for iron-stilbene and FeCl₂ ·H ₂ O, ΔE=(+2.52±0.02) mm/sec and (+2.50±0.05) mm/sec, yield electric field gradients at the iron nucleus ofq _z=+9.7·10¹⁷ V/cm² and +9.6·10¹⁷ V/cm², whereq _z⊥H; Debyetemperatures of θ=162 °K and 188 °K are obtained. The energy of the excited 3d-electron levels in iron-stilbene is estimated to Δ₁=309 cm^?1 and Δ₂=618cm^?1 as deduced from the temperature dependence ofΔE. In contrast to the suggestion ofEuler andWillstaedt bivalence of the iron in ironstilbene is found; its composition is shown to be 4(FeCl₂ ·H ₂O)·stilbene.     

Winkelverteilung der Kernphotoreaktion3He (γ,p)2H

The angular distribution of the photonuclear reaction³He(γ,p)²H was measured with an exitation energyE _x=16 to 27 MeV using a 32.5 MeV betatron. In agreement with a theoretical calculation of Böschet al. we found for the coefficients of the distributionf(θ)=b (a/b+sin²θ(1+β·cosθ+γ·cos²θ)) the values:a/b≦0.14; β=0.77 (+0.14; ?0.07); γ≦0.30. This was the first attempt to use spark chambers as a detection device for photonuclear reactions in the low energy range. We found it to be a promising new facility.     

Internal conversion coefficients in the Hartree-Fock atomic model. Calculations and experiments for199Hg

The internal conversion coefficients were calculated for the transitions in¹⁹⁹Hg using both Hartree-Fock and Hartree-Fock-Slater atomic models. The relative conversion line intensities were measured with the magnetic spectrometers in Prague and Heidelberg. The multipolarities were determined to be:M1+(0.20±0.03)%E2, pure E2 and M 1+ (13.4 ±0.4)%E2 for the 50, 158 and 208 keV transitions, respectively. Allowing for the nuclear structure effect in M1 component we obtained: M1+(0.15±0.03) %E2,λ = 2.4±1.0 for the 50 keV and M1+ (10.9±0.7)% E2, λ=3.8±0.5 for the 208 keV transitions. Very good agreement was found between theory and experiment for the atomic subshells,K, L_1?3,M _1?5,N, andO + P.     

Hybridization and electron interaction in nickel compounds

The bare Coulomb interaction, defined by the reaction 2dⁿ = d^n?1 + d^{n + 1} ? U is determined for some Ni compounds. It is found that U is larger than the 3d bandwidth even for metallic compounds. More relevant to the metal nonmetal transition is the optical gap energy E_G = U ? (E(3d^n?1) ? E(L)) where E(3d^n?1) and E(L) are the d-electron and ligand electron ionization potentials respectively.     

Negative Ions,Ozone, and Metastable Components in dc Oxygen Glow Discharge

In a dc glow discharge in oxygen, the concentrations of minor components of O₂(a¹Δ_g), O₂(b¹ Σ_g), O₃, O(¹D), as well as nagative ions and electrons have been measured. Balance equations have been derived which describe satisfactorily the stationary concentrations of these components as functions of gas pressure and discharge current. For the first time, the rate constants of important aeronomical reactions (a) O^? + O₂(a¹Δ_g) → O₃ + e, (b) O₂^? + O₂(a¹Δ_g) → 2O₂ + e and (c) e + O₃ → O₂^? +O have been measured as functions of gas temperature T and mean energies of ions E_i and electron E₆: K_a = (2.5 ± 0.5) · 10^?9 · (T/300)^{4 ± 0.4}· (E_i/0.04)^{?2.6 ± 0.4} cm³/s for T = 385?605 K and E_i = 0.10 ? 0.66 eV; K_b = (1.0 ± 0.3) · 10^?10 · (T/300)^{?2 ± 0.5} · (E_i/0.04)^{0.23 ± 0.05} cm³/s for T = 330?605 K and E_i = 0.09 + 1.5 eV; K_c for E_e = 0.8÷5 eV.     

Nuclear magnetic relaxation by self-diffusion in solid lithium:T 1-frequency dependence

We report on measurements of the⁷Li nuclear spin relaxation timeT ₁ in solid lithium as a function of temperature (?170°C≦T≦+180°C) and Larmor frequency (450kHz≦v _Li≦31.5 MHz). Using a relaxation model developed by Wolf and Cavelius and combining it with Seeger's diffusion formalism, the diffusion parameters for mono-and divacancy migration were evaluated by a least squares fit to the newly obtainedT ₁ data as well as to previousT _1? measurements. The result for the self-diffusion coefficientD ^SD is given byD ^SD=D ₁₀·exp(?Q ₁/RT)·[1+D ₂₁·exp(?Q ₂₁/RT)], withD ₁₀=0.038 cm²s^?1,Q ₁=12.0 kcal mol^?1,D ₂₁=250,Q ₂₁=4 kcal mol^?1 andR=1.98₅·10^?3 kcal mol^?1 degree^?1. Due to the flexibility of Seeger's formula, which contrasts with the standard Arrhenius interpretation of diffusion, discrepancies between earlier high- and low-frequency NMR investigations were eliminated. Furthermore, an excellent agreement with available results from tracer experiments was achieved by taking into account the theoretical predictions of the isotope effect and the vacancy correlation factor.     

Electron-nuclear double resonance of cubic 55Mn2+ in GaP

ENDOR measurements were used to determine the cubic crystal field splitting parameter a, and the nuclear spin-Hamiltonian parameters A, g_Nβ_N and U of the cubic ⁵⁵Mn²⁺ centre in GaP at 4.2K.     

Winkelkorrelationsmessungen an >30y Holmium 166 und Bestimmung desg R -Faktors des 4+-Rotationsniveaus von Erbium 166

The spins of several excited states of Er¹⁶⁶ have been investigated byγγ-angular correlation measurements. The spin sequence 0+, 2+, 4+, 6+ for the ground state rotational band was presumed to be correct. Unique assignments were derived for the states of 1076 keV, 1377 keV and 1785 keV asI=5, 7 and 6 respectively. These results are in agreement with the spins proposed byGallagher jr. andSoloviev. The multipolarities of theγ-transitions of 408 keV, 709 keV, 811 keV and 831 keV were derived as 95%E1+(5±1)%M2, 99·6%E1+(0·4±0·5)%M2, 99·1%E2+(0·9±0·3)%M1, and 96·1%E2+(3·9±1)%M1 respectively. The unusual mixing ratios of the transitions of 811 keV and 831 keV can be understood as a consequence of theK-selection rule. Eachγ-transition from the 1785 keV state should be stronglyK-forbidden and one expects a half-life ofT _1/2≈3·10^?9s. A measurement of the time spectrum of the coincidences between theβ-radiation and the high energyγ-lines gave however:T _1/2(1785 keV state)≦3·10^?10s. The rotation of the angular correlation between the 184 keV line and theγ-group at 820 keV has been measured in an external magnetic field of 53000 gauss as:ω·τ(4+)=0·083±0·006. This value contains small corrections for an additional rotation of the angular correlation of the 831 keV–184 keV triple cascade in the 6+state and for a small attenuation by internal fields. WithT _1/2(4+state)=1·23·10^?10s, andβ=7·08 one gets for theg-factorg _R=+0·266±0·024 in good agreement with recent results for the 2+ state.     

Ionization cross sections and rate coefficients for the ground state of AsI-like ions

Detailed level-by-level calculations of cross sections and rate coefficients for electron impact direct ionization and excitation-autoionization of AsI-like ions in the 3d ¹⁰4s ²4p ³ (⁴S_3/2) ground state have been performed. The cross sections are presented in the energy range near the threshold for the five ions Mo⁹⁺, Xe²¹⁺, Pr²⁶⁺, Dy³³⁺ and W⁴¹⁺. The rate coefficients are given for all the ions from Sr⁵⁺ to U⁵⁹⁺ in the AsI sequence at the seven electron temperatures (k T _e = 0.1E _I ,0.3E _I ,0.5E _I ,0.7E _I ,E _I ,2E _I and 10E _I , where E _I is the first ionization energy). The calculations include the contribution of direct ionization (DI) calculated using the Lotz formula approximation and the contributions of excitation-autoionization (EA) computed in the framework of the Distorted Wave (DW) approximation for the 4s ? nl, 3d ? nl and 3p ? nl resonant inner-shell excitations. The ionization enhancement due to the EA channels is presented as a function of Z along the AsI isoelectronic sequence. The present results show the great importance of the EA processes; an ionization enhancement factor of up to 6.5 is predicted for instance for Dy³³⁺ (Z = 66) at electron temperature of coronal equilibrium maximum abundance.     

Temperature dependence of the ESR spectra of Mn2+ in iron pyrite (FeS2)

The first observation of the ESR spectra of Mn²⁺, entering substitutionally for Fe²⁺ in the Van Vleck paramagnet FeS₂ (polycrystals), is reported. The data from 5 to 295 K fits the spin-Hamiltonian $\text{h}{}_{\mathrm{s}}\text{= gβ}\text{H}\text{·}\text{S}$ + $\text{[S}{}^{\mathrm{<mtext>2</mtext>}}{}_{\mathrm{z}}\text{?}\text{1}\text{3}\text{S(S + 1)] + A}\text{S}\text{·}\text{I}$, with g = 2.000 ± 0.001, A/β = ?95.0 ± 0.5 Oe and D/β varying from 50 Oe (5K) to 59 Oe (295 K). The temperature dependence of D can be described in terms of a single phonon-mode with frequency ? 145 cm^?1.     

Low-energy transition depopulating the isomeric 8+ level in 208Po

Conversion electron measurements of the low-energy transition depopulating the isomeric 8⁺ level in ²⁰⁸Po yielded E_γ = 4025 ± 20 eV and the conversion intensity ratios N₁/N₂ ? 0.2, N₂/N₃ = 0.75 ± 0.10, N_4.5/N₃ ? 0.2, O/N₃ = 0.35 ± 0.10, P/N₃ ? 0.1 and N₃/M₃ = 0.4 ± 0.2. These ratios are in accord with our calculations for the E2 multipolarity and exclude all other multipolarities with L ≦ 4. The total conversion coefficient was calculated to be 1.31 × 10⁷.