Paramagnetische Resonanz des dreiwertigen Gadoliniums in YPO4, YVO4 und YAsO4

The EPR spectra of Gd³⁺-doped isostructural single crystals of YPO₄, YVO₄, and YAsO₄ have been measured in X-band at room temperature and at nitrogen and helium temperatures. The zero-field splitting can be described by the five crystal-field parametersb ₂ ⁰ ,b ₄ ⁰ ,b _6/0,b ₄ ⁴ , and b ₆ ⁴ fitted to a tetragonal spin-Hamiltonian corresponding to the point symmetry D_2d of the Gd³⁺ site. The values ofg and b ₂ ⁰ vary significantly with host lattice and with temperature.     

Gyromagnetic ratios of 4+ and 6+ states in156Gd and158Gd

The followingg-factors have been derived from time integral measurements of γ-γ angular correlations in the static magnetic hyperfine field of magnetized gadolinium metal probes:¹⁵⁶Gd:g(4 ₁ ⁺ )=+0.310(19)g(6 ₁ ⁺ )=+0.25(21)g(4 ₃ ⁺ , 1511 keV)=+0.809(27)¹⁵⁸Gd:g(4 ₁ ⁺ )=+0.409(15). The 5.35d ¹⁵⁶Tb sources were produced by the reaction¹⁵⁶Gd(d, 2n)¹⁵⁶Tb in our cyclotron. A carrier-free 150y ¹⁵⁸Tb source was obtained from ISOLDE/CERN. In comparison with the precisely knowng-factors of the 2 ₁ ⁺ states,g(2 ₁ ^su+ ,¹⁵⁶Gd) =+0.386(4) andg(2 ₁ ⁺ ,¹⁵⁸Gd)=0.381(4), we observe a large reduction for the¹⁵⁶Gd 4 ₁ ⁺ state whereasg increases slightly for¹⁵⁸Gd. The half-life of the 4 ₁ ⁺ state of¹⁵⁸Gd was remeasured as¹⁵⁸Gd:T _1/2(4 ₁ ⁺ )=148(2) ps. A measurement of the rotation in the 4 ₃ ⁺ state of¹⁵⁶Gd in external magnetic fields of various strengths up toB _ext=9.5 T did not confirm the anomalous dependence of the magnetic hyperfine field in gadolinium metal on the external field, which has been reported by Persson et al. [29].     

The nucleon structure functions in deep inelastic scattering off deuterium: nuclear shadowing and the Gottfried sum rule

The perturbative QCD is applied to calculation of nuclear shadowing correction to the deuterium structure functionF ₂ ^D (x) atx«1. This correction is shown to be numerically large. It is emphasized that the neglect of nuclear shadowing leads to underestimating of the neutron structure functionF ₂ ⁿ (x) and, as a result, to gross overestimating of the Gottfried integral \(\int_0^1 {\left[ {F_2^P (x) - F_2^n (x)} \right]} dx/x\)      

Semiempirical investigation of perturbations of the g factors of electronic-vibrational-rotational levels of hydrogen: III. The r 3Π g − and s 3Δ g − states of the H2 and D2 molecules

The g factors of rovibrational levels of the (4d)r ³Π _g ^? and (4d)s ³Δ _g ^? states of the H₂ and D₂ molecules have been obtained for the first time. These values were found within the nonadiabatic model taking into account the interaction of the 4dπ³Π_g and 4dδ³Δ_g states in the pure precession approximation using semiempirical values of the expansion coefficients of the wave function in an adiabatic basis, which was obtained for the first time for the states of the triplet 4d complex of terms of the hydrogen molecules, and the results of numerical calculation of the overlap integrals of the vibrational wave functions of these states. It is established that the interference effects of the interaction between the 4dπ³Π _g ^? and 4dδ³Δ _g ^? states lead to significant (up to 7 times for the r ³Π _g ^? state of the H₂ and D₂ molecules and 70 and 8 times for the s ³Δ _g ^? state of the H₂ and D₂ molecules, respectively) differences between the nonadiabatic values of the g factors and the corresponding adiabatic values. It is found that the perturbed values of the g factors are much closer to the values corresponding to the case of Hund’s d coupling of angular momenta than to the values corresponding to the b coupling. It is established that the perturbations of the g factors of rovibrational levels of the states of the 4d complex of terms are much greater (up to 2 times for the ³Π _g ^? states and 350 times for the ³Δ _g ^? states) than the perturbations of the same characteristics for the 3d complex of terms of the hydrogen molecule with the same vibrational and rotational quantum numbers.     

Gyromagnetic ratios of excited states in186W

The gyromagnetic ratios of the 4 ₁ ⁺ , 6 ₁ ⁺ , and 2 ₂ ⁺ states in¹⁸⁶W were measured relative to that of the 2 ₁ ⁺ level by means of the transient field implantation perturbedγ-ray angular distribution technique. The nuclei in the states of interest were Coulomb excited using a beam of 220-MeV⁶³Cu projectiles and recoiled swiftly through a thin, polarized Fe foil. The present measurements yielded ratiosg(4 ₁ ⁺ )/g(2 ₁ ⁺ )=1.04±0.07,g(6 ₁ ⁺ )/g(2 ₁ ⁺ )=1.03 ±0.20 andg(2 ₂ ⁺ )/g(2 ₁ ⁺ )=0.63±0.13. The sizable disparity between the measuredg-factors of the ground- and excited-band is examined within the context of the interacting boson approximation model.     

Observation of perturbations in the rovibronic transition probabilities for the (4d)r 3Π g − , (4d) s 3 Δ g − → (2p) c 3Π u ± band systems of the H2 molecule

The ratios of the radiative transition probabilities for the lines of the P, Q, and R branches of the (4d)r ³Π _g ^? , (4d)s ³Δ _g ^? → (2p) c ³Π _u ^± band systems of the H₂ molecule have been measured for the first time. Significant (to two orders of magnitudes) differences are found between the experimental values and the adiabatic theory predictions. It is established that the results of the nonadiabatic calculation performed by us in the pure-precession approximation taking into account the electronic-rotational interaction of the 4d ³Π_g and 4d ³Δ_g states are in agreement with the experimental data. The optimal energies of rovibronic levels of the r ³Π _g ^? , s ³Δ _g ^? , c ³Π _u ^? , and c ³Π _u ⁺ states have been found and reidentification of 11 from 54 spectral lines, assigned previously to the (0-0) and (1-1) bands, was performed.     

Spin states of cobalt and the thermodynamics of Sm1 − x Ca x CoO3 − δ solid solutions

In the rare-earth SmCoO₃ perovskite, Co³⁺ ions at low temperatures appear to be in the low-spin state with S = 0, t _2g ² e _g ⁰ . If Ca²⁺ ions partially substitute Sm³⁺ ions, oxygen deficient Sm_{1 ? x} Ca _x CoO_{3 ? δ} solid solutions with δ = x/2 appear. The oxygen deficiency leads to the formation of pyramidally coordinated cobalt ions Co _pyr ³⁺ in addition to the existing cobalt ions Co _oct ³⁺ within the oxygen octahedra. Even at low temperatures, these ions have a magnetic state, either S = 1, t _2g ⁵ e _g ¹ or S = 2, t _2g ⁴ e _g ² . At low temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _pyr ³⁺ ions. Owing to the characteristic features of the crystal structure of the oxygen deficient perovskite, these ions form a set of nearly isolated dimers. At high temperatures, the magnetization of Sm_{1 ? x} Ca _x CoO_{3 ? δ} is mainly determined by the response of Co _oct ³⁺ ions, which exhibit a tendency to undergo the transition from the S = 0, t _2g ⁶ e _g ⁰ state to the S = 1, t _2g ⁵ e _g ¹ or S = 2, tt _2g ⁴ e _g ² state. In addition, the magnetization and specific heat of the solid solutions under study include the contribution from the rare-earth subsystem, which undergoes a magnetic ordering at low temperatures.     

Microscopic foundation of the interacting boson model in thes d-shell nuclei

Starting from an isospin invariant shell-model hamiltonian, we describe a method for deriving microscopically the IBM-hamiltonian appropriate to lights d-shell nuclei. The key ingredients of our approach are:a) the Belyaev-Zelevinsky-Marshalek (BZM) bosonization procedure;b) two successive unitary transformations that extract the “maximally decoupled” collective bosons with angular momentaJ=0(s _ππ ⁺ ,s _νν ⁺ ,s _πν ⁺ ) andJ =2(d _ππ ⁺ ,d _νν ⁺ ,d _πν ⁺ (T=0),d _πν ⁺ (T=1)). The method is applied to obtain the low-energy spectra and the electron scattering form factors for the 0 ₁ ⁺ →2 ₁ ⁺ transitions in²⁰Ne and²⁴Mg. Good agreement with the exact shell-model results is achieved. The inclusion of proton-neutron bosons (s _πν ⁺ ,d _πν ⁺ (T=1),d _πν ⁺ (T=0)), as well as the renormalization of boson parameters due to the non-collective degrees of freedom, are shown to play a crucial role.     

Comparative study of the semiempirical three-parameter potential energy functions for diatomic molecules

A comparative study is made of four three-parameter semiempirical potential energy functions for 32 electronic states of diatomic molecules and their ions:n ₂:X¹gS _g ⁺ ,B ³π_g,A ³ gS_u,C ³ _u,B′ ³ gS_u.a ¹ π_g, a′gS _u ^? ,Ω ¹δ_u N ₂ ⁺ :X ² gS _g ^gS +A ² π,C ² gS _u ⁺ ,B ² gS _u ⁺ CO:X¹gS⁺,a ³ π, a′³ gS_u,e ³ gS^?,d ³gD₁,A ¹π CO⁺:X²gS⁺,A ² π,B ²gS⁺ O₂:X³gS _g ^? ,B ³ gS_u,c ¹ gS _u ^? ,b ¹gS _g ^s ,a ¹ δ_g,c ³ δ_u O ₂ ⁺ :X ²π_g,A ² π_g, a¹ π_g,b ⁴ gS _g ^? A program for numerically integrating the radial Schrödinger equation by the Cooley method is worked out. Certain additional units are introduced to conserve computer time. The resulting vibrational levels are compared with the experimental levels for all the electronic states studied. It is concluded on the basis of this analysis that it is not possible to describe equally well all the electronic states of various molecules on the basis of any single three-parameter potential function. A method for choosing a potential function for describing some particular electronic state of a diatomic molecule is proposed.     

Ab initio calculation of transition dipole moments for transitions between valence states in oxygen molecules

Results of ab initio calculations of potential-energy curves for 20 singlet and 20 triplet valence states of oxygen with configuration interaction taken into account in the 6-31G basis are presented. Transition dipole moments of triplet-triplet (1³Π_g ← B ³Σ _u ^? , 1³Π_g ← A ³Σ _u ⁺ , 1³Π_g ← A′ ³Δ_u, B ³Σ _u ^? ← X ³Σ _g ^? , 2³Π_u ← 1³Π _g, 2³Σ _g ^? ← B ³Σ _u ^? , 1³Π_u ← X ³Σ _g ^? , 2³Π_u ← X ³Σ _g ^? , 2³Π _g ← A′³Δ_u, 3³Π_g ← A′ ³Δ _u, 2³Δ_u ← 2³Π_g, 3³Π_g ← B ³Σ _u ^? , and 2³Π_g ← A ³Σ _u ⁺ ) and singlet-singlet (2¹Σ _g ⁺ ← 2¹Π_u, 2¹Π_u ← 1¹Π ^g, ¹Π_u ← 2¹Δ_g, 1¹Π_g ← c ¹Σ _u ^? , ¹Π_u ← b ¹Σ _g ⁺ , 1¹Δ _u ← a ¹Δ_g, 2¹Π_u ← a ¹Δ_g, 2¹Δ_g ← 1¹Δ_u, ¹Π _u ← a ¹Δ _g, 1¹Π_u ← b ¹Σ _g ⁺ , 2¹Π_g ← 1¹Π_u, 2¹Π _g ← c ¹Σ _u ^? , 1¹Δ _u ← 1¹Π _g, f′Σ _u ⁺ ← b ¹Σ _g ⁺ , 2¹Σ _g ⁺ ← f ′¹Σ _u ⁺ , 3¹Π_g ← 1¹Δ_u) radiative transitions are calculated as functions of internuclear separation. The possibility of observing these transitions under experimental conditions is discussed.     

Pulse ENDOR studies on the radical pair P 700 +· A 1 ·− and the photoaccumulated quinone acceptor A 1 ·− of photosystem I

The secondary acceptor A₁ of the electron transport chain(s) of photosystem (PS) I is a phylloquinone (vitamin K₁, VK₁). Pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments at X-band frequencies were performed on the photoaccumulated acceptor radical A ₁ ^·? and the radical pair state P ₇₀₀ ^·+ A ₁ ^·? in PS I ofThermosynechococcus elongatus. The data obtained were compared with data from the respective radical anion of VK₁ in organic solvents. The unusualg tensor magnitude of A ₁ ^·? is explained by the hydrophobic binding pocket of this radical. The hyperfine couplings and the spin (and charge) density distribution is very different for A ₁ ^.? in PS I and VK ₁ ^·? in frozen alcoholic solution. This is attributed to a rather strong one-sided hydrogen bond to A ₁ ^·? . The presence of a hydrogen bond to A ₁ ^·? has only a minor effect ong. The hyperfine coupling constants of A ₁ ^·? determined from the radical pair spectra deviate only slightly from those derived from photoaccumulated A ₁ ^·? in PS I treated with dithionite at high pH. ENDOR resonances of the proton in a H bond were detected and an estimate of the strength and geometry of this bond to A ₁ ^·? was obtained. The significance of the hydrogen bond and other (hydrophobic) interactions of A₁ with the surrounding are briefly discussed.     

High-frequency EPR studies on cofactor radicals in photosystem I

Electron paramagnetic resonance (EPR) spectroscopy at W-band (94 GHz) is used to resolve theg-tensors of the radical ions of the primary chlorophyll donor P ₇₀₀ ^+? and the quinone acceptor A ₁ ^?? in photosystem I. The obtainedg-tensor principal values are compared with those of the isolated pigment radicals in organic solvents and the shifts are related to an impact of the protein environment. P ₇₀₀ ^+? has been investigated in photosystem I single crystals at 94 GHz. W-band EPR applied to the photoinduced radical pair P ₇₀₀ ^+? A ₁ ^?? is used to correctly assign theg-tensor axes of P ₇₀₀ ^+? to the molecular structure of the primary donor. Density functional theory calculations on a model of A ₁ ^?? in its binding pocket derived from the recent crystal structure of photosystem I were utilized to correlate experimental magnetic resonance parameters with structural elements of the protein.     

Vacuum energy ingϕ d /4 -theory forg→∞

In the nonlocalg? _d ^/4 (d≧1) and localg? ₂ ⁴ theory theS-matrix is obtained in a form of the functional integral which is proved to exist. The density of vacuum energy $$E(g) = - \mathop {\lim }\limits_{V \to \infty } \frac{1}{V}\ln \left\langle {0\left| {S_V (g)} \right|0} \right\rangle $$ is investigated. It is proved to be analytic through the whole complexg-plane except for the negative real axis and pointg=0. Its asymptotic behaviour forg→∞ is found.     

EPR of a fullerene-molecule-derived paramagnetic center as a mesoscopic conducting object

Discussion of theg-factor value of fullerene is based on the model of itinerant electrons restricted to the surface of the fullerene molecule C₆₀. The Ag shift, i.e., the difference between the experimentalg-factor and theg-factor of free electron Δg = g ? 2.0023 for C ₆₀ ^?1 is negative as for a very small metallic conducting particle.g-factor value is proportional to the interaction between itinerant electrons in the conduction band, thus the Δg is negative for C ₆₀ ^?1 and C ₆₀ ^?3 having less than half filled conduction band, while Δg is positive for C ₆₀ ⁺ where the conduction band is almost filled.     

g-factor of the 4 1 + rotational state of160Dy

By use of Ge-detectors of the OSIRIS-collaboration [1] in connection with the 12 detector IPAC apparatus of our laboratory [2] a precise measurement of theg-factor of the 4 ₁ ⁺ rotational state of¹⁶⁰Dy was performed. The directional correlations of the threeγ-γ cascades, 1003-197 keV, 1103-197 keV and 1115-197 keV, which are weakly populated in the decay of 72.3 d¹⁶⁰Tb were observed simultaneously. The integral rotations in the static hyperfine field of DyTb at 4.2 K were measured. Theg-factorg(4 ₁ ⁺ )=+0.350(20) was derived. By comparison with the magnetic splitting of the 2 ₁ ⁺ rotational state observed in the same environment by a Mössbauer experiment [3] the ratio of the twog-factors was derived as g(4 ₁ ⁺ )/g(2 ₁ ⁺ )=+ 0.91(5). For the high energy lines we derived from the measured directional correlations the E1/M2 mixing parameters: δ(1003 keV)=+0.005(4); δ(1103 keV)=?0.020(22), and δ(1115 keV)=+0.010(4)     

g-factors of the lowest 2+ and 4+ states in198, 200, 202Hg

Theg-factors of the 2 ₁ ⁺ and 4 ₁ ⁺ states in^198,200,202Hg were simultaneously measured by means of the transient-field perturbed angular correlation method in Coulomb excitation using multi-isotopic targets and thin polarized Gd foils as ferromagnetic host. Theg(2 ₁ ⁺ ) andg(4 ₁ ⁺ ) were found identical within errors in^{198, 200}Hg, while in²⁰⁰Hg lowerg-factor values have been determined. The experimentalg-factors were compared with the predictions of the pairing-plus-quadrupole, dynamical deformation and interacting boson models.     

The magnetic moment of the 10+ isomer in140Ce andE1 transitions inN=82 isotones caused by outer subshell configurations

Using the reaction¹³⁸Ba(α,2n)¹⁴⁰Ce the magnetic moment of the 10 ₁ ⁺ isomer atE _x =3714.7 keV in theN=82 nucleus¹⁴⁰Ce has been determined by means of the TDPAD method toμ=+10.3(4)μ _N . Measuredg-factors in¹⁴⁰Ce are compared to calculations within the shell model with configuration mixing. For the 10 ₁ ⁺ isomer in¹⁴⁰Ce the four proton configuration π(1g ₇ ^2/2 ,2d ₅ ^2/2 ) has been found to be dominant. From theg-factor measurement strong contributions of multiparticle excitations to thegp2d _3/2,π3s ₁ ² or π1h ₁₁ ² shells and admixtures of neutron excitations to the wave function of the 10 ₁ ⁺ state could be excluded. The strongE1γ-branch of the deexcitation of the 10 ₁ ⁺ isomer in¹⁴⁰Ce can be explained by means of small admixtures of configurations which contain the outer subshell excitationsπ2f _7/2 andπ1h _9/2. On this basisE1 transitions experimentally observed in theN=82 nuclei¹⁴⁰Ce,¹⁴¹Pr and¹⁴⁵Eu may be understood.     

Hyperfine structure of the atomic osmium spectrum: Superposition of configurations and the effect of nucleus volume

The contributions of the superposition of configurations ns ²5d ⁷6s+ns5d ⁷6sn′s+ns5d ⁷6s ² (n=1–5, n′=7–10) to the parameters of the hyperfine structure a _5d ⁰¹ , a _5d ¹² , a _5d ¹⁰ , a _6s ¹⁰ in the spectrum of the osmium atom Os I are calculated. Nonzero contributions are shown to be made only to the parameters a _5d ¹⁰ and a _6s ¹⁰ . This fact justifies the inclusion of the parameter a _5d ¹⁰ in the semiempirical analysis of experimental values of magnetic dipole constants of the hyperfine structure of the 5d ⁷ s configuration in the spectrum of the osmium atom. The effect of nucleus volume on the parameters of the hyperfine structure in the spectra of osmium isotopes ¹⁸⁷Os and ¹⁸⁹Os is estimated.     

Evidence for a 3.6 minute isomeric 12− state of the πh 11 2/−1 vi 13 2/−1 configuration in206Tl and effective two-particle interactions

Using the²⁰⁴Hg(α, pn)-reaction andα-particles of energies 39–55 MeV, we have found an isomeric 3.6 min 12^? state in²⁰⁶Tl at 2,642.9 keV which has the two-hole configurationπh ₁₁ ^2/?1 vi ₁₃ ^2/?1 The 12^? state decays mainly by anE5 transition of energy 1,021.4 keV to a 7⁺ state at 1,621.5 keV whose main configuration isπs ₁ ^2/?1 vi ₁₃ ^2/?1 There is, in addition, evidence for a weak 565 keVM 4 branch to an 8⁺ state at 2,078 keV whose main configuration should beπh ₁₁ ^2/?1 vf ₅ ^2/?1 . The 7⁺ state decays by a stretched cascade ofγ-rays to states of the following values ofJ ^π and excitation energy: 5 _? ⁺ , 1,405.4 keV; 4^?, 952.1 keV; 2^?, 265.8 keV and 0^?, 0 keV. The main configurations of these states areπh ₁₁ ^2/?1 vp ₁ ^2/?1 ,πd ₃ ^2/?1 vf ₅ ^2/?1 ,πd ₃ ^2/?1 vp ₁ ^2/?1 andπs ₁ ^2/?1 vp ₁ ^2/?1 respectively. From the nuclear masses of²⁰⁸Pb,²⁰⁷Pb,²⁰⁷Tl, and²⁰⁶Tl and the experimental excitation energies it is possible to obtain the proton hole-neutron hole interaction in²⁰⁶Tl. This interaction is compared with the calculations of Kuo and Herling and the discrepancies are discussed. The 12^?→8⁺ M4 transition rate is reduced because of destructive interference between the protonh _11/2→d _3/2 and the neutroni _13/2→f _5/2 contributions. The magnitude of the reduction is accurately reproduced by the wave functions of Kuo and Herling. The 12^?→7⁺ E5 transition rate is about twice as large as the single-holeπh ₁₁ ^2/?1 πs ₁ ^2/?1 transition rate. This deviation is fully explained by the configuration admixtures in the 7⁺ state, given by Kuo and Herling.     

EPR investigations of SiC and SiOC nanometric powders

EPR investigations are performed in SiC and SiOC nanometric powders annealed between 1200 and 1800°C. By using different EPR frequency bands and a suitable spectra analysis, three quite different paramagnetic defects with well defined $\tilde g_i $ (i=1, 2, 3) and hyperfine $\tilde A_i $ (i=1, 2) tensors account for the EPR signal in these materials. The defects are characterized by $\tilde g_1 $ (g ₁ ^‖ =2.0046(3), g ₁ ^? =2.0023(3)), $\tilde g_2 $ (g ₂ ^‖ =2.0037(3), g ₂ ^? =2.0028(3)) and isotropic $\tilde g_3 $ (2.0030(3)) tensors. In SiC powders, the defects assignment is discussed with respect to the different SiC forms, namely α-SiC and β-SiC polytypes as well as amorphous SiC and carbon present in minor concentration in the network. In SiOC powders, the above defects are evidenced only at high annealing temperature (T _a≥1200°C) when the oxygen contained is highly reduced.