Hole centers in γ-irradiated,oxidized Al2O3

ESR observations of centers with $\text{S =}\text{1}\text{2}\text{, g ? 2, S = 1, g ? 2}$ have been made at 77 K on oxidized Al₂O₃ after γ-irradiation at 30°C. From the radiation growth data, it is shown that the $\text{S =}\text{1}\text{2}$ centers are precursors of the S = 1 centers. In addition, when the S = 1 centers anneal out at about 110°C, the $\text{S =}\text{1}\text{2}$ centers reappear and eventually anneal out at about 260°C. Previously Gamble and Cox, respectively, observed $\text{S =}\text{1}\text{2}$ and S = 1 paramagnetic centers in electron-irradiated nominally pure Al₂O₃ and γ-irradiated, oxidized, titanium-doped Al₂O₃. The models proposed for these centers were one hole and two holes trapped on oxygen ions adjacent to Al³⁺ vacancies. Our results further substantiate these models.     

EPR and magnetic susceptibility studies of xCuO·(1−x)[2B2O3·Li2O] glasses

The results of EPR and magnetic susceptibility studies on xCuO·(1?x)? [2B₂O₃·Li₂O] glasses with $\text{0?x?30 mol \%}$, are reported. The modification of EPR spectra with the increasing of CuO content are explained supposing that these are the result of the superposition of two EPR signals, one showing the hyperfine structure typical for isolated Cu²⁺ ions and other consisting from a broad line centered at g ～ 2 typical for the clustered Cu²⁺ ions. The values of the EPR parameters prove that the coordination of isolated Cu²⁺ -complexes remains approximately the same and show that Cu²⁺ ions are situated in axially distorted octahedral vicinities. EPR measurements have shown that the Cu²⁺ ions are present mostly as the isolated species when $\text{x?5 mol \%}$. Beside the dipole-dipole coupling between Cu²⁺ ions, the magnetic measurements suggest that for x>10 mol % superexchange interactions appear, too. From Curie constant is established that in this glass system the copper ions are in Cu²⁺ and Cu⁺ valence states. Also, the amounts of the copper ions in bivalent state are determined.     

Shallow acceptor bound exciton and free exciton states in high-purity zinc telluride

We investigated excitons bound to shallow acceptors in high-purity ZnTe and measured excitation spectra of two-hole luminescence lines at 1.6 K using a tunable dye-laser. The electron-hole coupling in the bound exciton (BE) states appears to be very different for the various acceptors even for almost identical exciton localisation energies. Three different types of BE are reported. For the Li-acceptor BE we observe three sub-components separated by 0.22 and 0.17 meV and interpreted as J = $\text{1}\text{2}$, $\text{3}\text{2}$, $\text{5}\text{2}$ states. The Ag-acceptor BE exhibits a strong ground state and a weak excited state at 1.3 meV higher energy. For the as yet unidentified k-acceptor we observe a single BE level, degenerate with the Ag-acceptor BE ground state. Dips in the excitation spectra due to absorption into free exciton 1S, 2S, and 3S states yield an exciton Rydberg R₀ = 12.8±0.3 meV and a free exciton binding energy FE(1S) = 13.2±0.3 meV.     

V4+ in SrTiO3: A Jahn-Teller impurity

EPR results of V⁴⁺, with $\text{S =}\text{1}\text{2}$, in SrTiO₃ are reported. The tetragonal local symmetry of the impurity ion is related to strong T_2g × ?_g coupling as evidenced by intensity variations in the presence of stress. At 4.2 K the V⁴⁺ EPR behaviour is related to the intrinsic local strain in SrTiO₃.     

Mössbauer and magnetic studies of BaVS3 and V5S8 doped with 57Fe

Iron can be easily introduced in BaVS₃ and V₅S₈. It is located at the vanadium sites and has been used as a probe to analyse by Mössbauer effect the magnetic properties of its surrounding matrix. The electronic state of iron in this matrix has also been studied. It was found that in BaVS₃, the iron is in a low spin Fe³⁺ configuration $\text{(S =}\text{1}\text{2}\text{)}$. In V₅S₈ at 4.2 K, the iron is in low spin Fe²⁺ configuration (S = 0). The rapid decrease of quadrupole splitting observed between 50 and 200 K is attributed to a thermally activated change in electronic structure. The high temperature configuration (above 200 K) seems to be neither pure low spin Fe³⁺ nor high spin Fe²⁺, but a mixture of configurations fluctuating at a rate which is faster than the characteristic time of Mössbauer measurements.     

Magnetic resonance investigations of the infrared levels of photoexcited Nd+3 in LaCl3

The observation of a photoexcited EPR signal from the lowest Stark level of the ⁴I_{$\text{11}\text{2}$} state of Nd⁺³ in LaCl₃ crystal at 4.2°K suggests a rapid relaxation process within the infrared states of Nd⁺³.     

Final state interactions in deuteron breakup by protons at 585 and 800 MeV

Neutron-proton final state interactions (FSI) were observed in the deuteron breakup reaction ²H(p, 2p)n-via a kinematically complete experiment at incident proton energies of 585 and 800 MeV. Kinematic conditions were chosen which allowed the final state proton and neutron to have small relative energies; data were taken at four proton c.m. scattering angles at 800 MeV, ranging from 71° to 119° and at 94° and 106° at 585 MeV. The data are analyzed in terms of the Goldberger-Watson formalism for final state interactions, and the individual contributions of the ¹S₀ and ³S₁ np states are determined. The ${}^3\text{S}{}_1{}^1\text{S}{}_0$ ratio is large, as expected from some reaction models. The ratio of ³S₁ (almost elastic) to pd elastic cross sections is in good agreement with FSI analysis.     

Characterization of LiFeCl4 and AgFeCl4 ionic conductors

LiFeCl₄ and AgFeCl₄ are obtained by direct reaction between LiCl or AgCl and FeCl₃ at 300°C and 400°C respectively. Both compounds are monoclinic with $\text{a = 7.02 (1)}\text{A}\text{?}$, $\text{b = 6.33 (1)}\text{A}\text{?}$, $\text{c = 12.72 (4)}\text{A}\text{?}$, β = 92° (30') for LiFeCl₄ and $\text{a = 10.60 (5)}\text{A}\text{?}$, $\text{b = 6.30 (5)}\text{A}\text{?}$, $\text{c = 12.34 (10)}\text{A}\text{?}$, β = 106° (1) for AgFeCl₄.LiFeCl₄ is clearly isotypic of LiAlCl₄. Magnetic measurements characterize in both cases Fe³⁺ ions in a high spin tetrahedral situation. LiFeCl₄ becomes antiferromagnetic at low temperature (T_N?10 K). AgFeCl₄ reveals a more complex situation. On contrary to the silver derivative, LiFeCl₄ is a good ionic conductor with activation energy of 0.78 eV in the solid state below 105°C, and a sharp increase in the lithium mobility at this temperature.     

Mean lifetimes of excited levels of Ar II. I. Time correlation measurements

Mean Lifetimes of excited levels of Ar II have been measured using the method of time-correlated photons in cascade. The following results were obtained: for 4p⁴S^°_{$\text{3}\text{2}$}, τ = 7·2±0·3ns; for 4p′²F^°_{$\text{7}\text{2}$}, τ = 8·8±0·2 ns; for 4p′²F^°_{$\text{5}\text{2}$}, τ = 8·0±0·2 ns. These results are compared with experimental and theoretical values.     

Long-lived non-equilibrium population of Fe3+ electronic states after the K-capture of 57Co

Mössbauer emission spectra of a frozen aqueous solution of ⁵⁷CoCl₂ show contributions from the $\text{S}{}_{\mathrm{z}}\text{= +}\text{5}\text{2}$ and the $\text{S}{}_{\mathrm{z}}\text{= +}\text{3}\text{2}$ Zeeman levels of Fe³⁺ ions at T = 4.2 K in H ? 30 kG. The K-capture results in a non-equilibrium state of relaxation time comparable to the lifetime of the nuclear excited state (～ 10^?7 s).     

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.     

A study of valency changes of vanadium ions in Al2O3 by γ irradiation

The effect of γ irradiation at 300 K on the concentrations of vanadium ions V³⁺, V⁴⁺ and V²⁺ in Al₂O₃ has been studied quantitatively, using three techniques: optical absorption (V³⁺), low temperature thermal conductivity measurements (V⁴⁺) and EPR (V²⁺). Several single crystals of Al₂O₃ doped with vanadium in a large range of concentration $\text{(2.8 × 10}{}^{18}\text{? 1.3 × 10}{}^{20}\text{at.}\text{cm}{}^3\text{)}$ have been measured. The evolution of the respective concentrations by γ irradiation as a function of the total vanadium content C is quite different in the two regions $\text{C< 1.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ and C larger than this value. A consistent analysis of the results has nevertheless been achieved, leading to the determination of the absolute concentrations of the three ions in the as-received and γ irradiated states for all samples with $\text{C<4.2 × 10}{}^{19}\text{at.}\text{cm}{}^3$ (room temperature annealing is observed above this value). The concentrations of V⁴⁺ and V²⁺ ions are always small, but V⁴⁺ ions are more stable: they are present in the as-received state at a level of 1% of the total concentration and a maximum value of $\text{/}\text{?}\text{2.3 × 10}{}^{18}\text{at.}\text{cm}{}^3$ is observed in the γ irradiated state; on the other hand there are less than 4.7 × 10¹⁵V²⁺ ions per cm³ in the as-received state and the maximum value is only $\text{4.2 × 10}{}^{17}\text{at.}\text{cm}{}^3$. Charge transfer between V ions only is not sufficient to explain the experimental results and other defects must be involved in the γ irradiation effect.     

s- and p-wave neutron spectroscopy: Part V. Level Spacings in Heavy Nuclei

Total neutron cross sections were measured for natural rubidium and thallium and for the separated isotopes, Pb²⁰⁸, Pb²⁰⁷, Pb²⁰⁶, Tl²⁰³, and Rb⁸⁵. Approximate s-wave resonance spacings were estimated for Pb²⁰⁷, Y⁸⁹, Rb⁸⁷, Rb⁸⁵, Tl²⁰³, and Tl²⁰⁵. D₀ = D_J(2J + 1) = 2D_S(2I + 1) = 50, 24, 8, 4, and 30 kev, respectively, where D_s is the average (s-wave) level spacing for all channels. The spacings (D₀) of Pb²⁰⁶ and Pb²⁰⁸ were found to be of the order of hundreds of kew; there is also evidence that resonance spacings are very wide for Sr⁸⁶ and Ba¹³⁶. It is concluded that, in all compound nuclei with a neutron number silightly less than the magic numbers 50, 82, and 126, the resonance spacings are usually not much less than when the magic number is exceeded slightly. Since neutron excitation energies of these sub-magic nuclei are higher than the average, the observed wide level spacings below the magic numbers must be due to the properties of the nearly closed shells and can not possibly be caused only by low excitation energy of the compound nucleus. In considering these comparisons it is shown that, for s-wave resonances, the relation $\text{D}{}_{\mathrm{J}}\text{=}\text{D}{}_0\text{(2J + 1)}$ is a useful approximation in that a plot of D₀ is a much less erratic function of A than is the observed spacing. We also discuss the Bethe-Hurwitz effect, i.e., the influence on resonance spacing (apart from the 2J + 1 factor) of an unpaired nucleon in the target nucleus. We estimate that $\text{α ≧ 30}$ in the equation $\text{D}{}_0\text{(0)}\text{D}{}_0\text{(W)}\text{=}\text{exp}\text{(αW)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ where D₀(0) is the energy and spin independent spacing parameter, and W is the excitation energy of the compound nucleus.     

Luminescence characteristics of Pb centres in undoped and Ce-doped Lu3Al5O12 single-crystalline films and Pb→Ce energy transfer processes

At 4.2-350 K, the steady-state and time-resolved emission and excitation spectra and luminescence decay kinetics were studied under excitation in the 2.5-15 eV energy range for the undoped and Ce³⁺-doped Lu₃Al₅O₁₂ (LuAG) single-crystalline films grown by liquid phase epitaxy method from the PbO-based flux. The spectral bands arising from the single Pb²⁺-based centres were identified. The processes of energy transfer from the host lattice to Pb²⁺ and Ce³⁺ ions and from Pb²⁺ to Ce³⁺ ions were investigated. Competition between Pb²⁺ and Ce³⁺ ions in the processes of energy transfer from the LuAG crystal lattice was evidenced especially in the exciton absorption region. Due to overlap of the 3.61 eV emission band of Pb²⁺ centres with the 3.6 eV absorption band of Ce³⁺ centres, an effective nonradiative energy transfer from Pb²⁺ ions to Ce³⁺ ions takes place, resulting in the appearance of slower component in the luminescence decay kinetics of Ce³⁺ centres and decrease of the Ce³⁺-related luminescence intensity.     

Frustrated magnetic structures: II. Antiferromagnetic structure of the ordered modified pyrochlore NH4FeIIFeIIIF6 at 4.2 K

The nuclear and magnetic structures of the ordered modified pyrochlore NH₄Fe²⁺Fe³⁺F₆ were solved at 4.2 K. NH⁺₄ tetrahedra are almost regular ($\text{〈}\text{N}\text{?}\text{H}\text{〉 =}\text{0.924}\text{A}\text{?}$) and the fluorinated skeleton at 4.2 K does not exhibit large deviations from the room-temperature positions (R_N = 0.042). Below T_N = 19 ± 1 K the magnetic and nuclear cells are identical. The strictly antiferromagnetic arrangement of Fe²⁺ spins (μ = 3.12(9)μB) along the [0 1 0] direction contrasts with the canted antiferromagnetic sublattice of Fe³⁺ ions (μ = 4.13 [8] μB) which is quasi-orthogonal (α = 76°) to the Fe²⁺ sublattice (R_mag = 0.078). The main component of Fe³⁺ moments lies along a. The antiferromagnetism of NH₄Fe³⁺Fe³⁺F₆ is compared to the spin-glass like behaviour which occurs when M²⁺ and M³⁺ ions are randomly distributed on the cationic sites.     

Electron paramagnetic resonance of Gd3 in YCl3·6H2O

The electron paramagnetic resonance spectrum of Gd³⁺ in YCl₃·6H₂0 with $\text{1}\text{100}$ dilution of Gd/Y ions, has been studied with an X-band spectrometer at 295, 77 and 1.77°K and with a K-band spectrometer at 295 and 77°K. The individual values of all the parameters are evaluated from the data at the three temperatures. In particular, the following values for the g-tensor and the zero-field splitting parameters b₂⁰ and b₂² are obtained from X-band data: at 295°K, g_zz = 1.994±0.005, g_xx = 1.992±0.005, g_yy = 1.997±0.005, b₂⁰ = 1.898 ±0.015 GHz, b₂² = ?2.247 ± 0.015GHz; at 77°K, g_zz = 1.999±0.008, g_xx = 2.000±0.008, b₂⁰= 1.978 ±0.022 GHz, b₂² = ?1.574±0.022GHz; at 1.77°K, g_zz = 2.002±0.010, g_xx = 1.990 ±0.010, b₂⁰ = 2.011 ± 0.025 GHz, b₂² = ?1.650 ±0.025 GHz. (The K-band values are found to be consistent with the X-band values). From the angular dependence of the data in the ZX plane (i) the angle X₀ which the Z axis makes with the a vector of the unit cell, is determined to be 58.00 ±0.25° and (ii) the existence of pseudo-symmetry axes at ±5° from the Z axis in the ZX plane as found by heat capacity and specific heat data has been confirmed. An estimate is also made of the extent of admixture of the excited ${}^6\text{P}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ state with the ground state ${}^8\text{S}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$.     

EPR of V2+ in SrCl2

The X-band EPR spectrum of SrCl₂:V has been measured at liquid nitrogen temperature. A signal associated with V²⁺ in a site of trigonal symmetry is observed. The EPR data have been explained using the spin hamiltonian $\textcolor{red}{}\text{= μ}{}_{\mathrm{\beta }}\text{H}\text{g}\text{?}\text{S}\text{+ D[S}{}^2{}_{\mathrm{z}}\text{?}\text{1}\text{3}\text{S(SH)] +}\text{S}\text{A}\text{?}\text{I}$, with D ? hv, g_∥ = 1.957 ± 0.004, g₆ = 1.954 ± 0.004, A_∥ = 230 ± 5 MHz, A₆ = 235 ± 5 MHz. This V²⁺ defect is similar to those previously reported in fluoride crystals with the fluorite structure.     

The properties of K and coadsorbed CO + K on Ru(001): I. Adsorption,desorption, and structure

An extensive photoemission and LEED study of K and CO+K on Ru(001) has been carried out. In this paper the LEED and some XPS results together with TPD and HREELS data are presented in terms of adsorption, desorption. and structural properties, and their compatibility is discussed. Potassium forms (2 × 2) and $\text{(}\text{3}\text{×}\text{3}\text{)R30°}$ overlayers below and near monolayer coverage, and multilayer bonding and desorption is similar to that of bulk K. The initial sticking coefficients for CO adsorption on K predosed surfaces are correlated with the initial K structure, and s₀ and CO saturation coverages decrease with increasing K coverage. Two well-characterized mixed CO+K layers have been found which are correlated with predosed (2 × 2) K and $\text{(}\text{3}\text{×}\text{3}\text{)R30°}\text{K}$. They have CO to K ratios of 3:2 and 1:1, and lead to LEED patterns with (2 × 2) and (3 × 3) symmetry, respectively. The molecule is believed to be sp² rehybridized under the influence of coadsorbed K, leading to stronger CO-Ru and weaker C-O bonds as indicated by the TPD and HREELS results, and to stand upright in essentially twofold bridges.     

Non-cubic Mn2+-centers in BaF2

The EPR spectra of thermally treated BaF₂: Mn samples is reported. After thermal annealing at 900 K a trigonal Mn²⁺ center with g=2.000±0.005, |D|=2725±40MHz, |A|=265±10MHz, $\text{D}\text{A}\text{>0}$, is observed. Annealing at 1200 K produces an orthorhombic Mn²⁺ center with g=2.00±0.01, |D|=2430±40MHz, |E|=570±20MHz, |A|=265±10MHz, $\text{D}\text{A}\text{<0}$. The superhyperfine (SHF) structures due to interactions with the neighbouring fluorines indicates that the trigonal manganese interacts with four fluorines, three of them equivalent. The orthorhombic Mn²⁺ shows interaction with four equivalent fluorine nuclei.     

Electron paramagnetic resonance of Ce3+ ions in lead thiogallate single crystals

The results of electron paramagnetic resonance (EPR) studies of Ce³⁺ impurity ions in single crystals of lead thiogallate PbGa₂S₄ have been reported. The Ce³⁺ ions substitute for Pb²⁺ ions in the crystal lattice of PbGa₂S₄. A number of paramagnetic cerium centers in lead thiogallate have been observed. The spectra are described by the spin Hamiltonian of rhombic symmetry with the effective spin S = 1/2. The g factors of the main cerium centers have been determined. A large number of paramagnetic centers are due to both nonequivalent positions of lead and local charge compensation under the substitution Ce³⁺ ?? Pb²⁺.