Spectra of multiquantum echo signals from quadrupole nuclei with half-integral spin in magnetically ordered materials

The numerical simulation of two-pulse echo signals at times 2τ, 4τ, and 6τ for the I=5/2 spin and at time 2τ, 4τ, and 8τ for the I=7/2 spin (τ is the time interval between exciting pulses) is carried out. It is shown that a delay by 2τ in the moment of formation of the echo results in the disappearance of extreme quadrupole satellites in the NMR spectrum obtained by recording the frequency dependence of the echo amplitude. The echoes at the maximum possible time of formation (2I+1)τ are only observed at the frequency of the purely magnetic spectroscopic transition $ \pm \frac{1}{2} \rightleftarrows \mp \frac{1}{2}$ ; no such echoes are observed at the quadrupole satellite frequencies. The computations are compared with the experimental results obtained for the ⁵⁵Mn nuclei (spin I=5/2) in the perovskite GdCu₃Mn₄O₁₂ and the spinel Li_0.5Fe_2.5O₄: Mn.     

High-spin states in27Al

The²⁴Mg(α, p γ) reaction has been studied atα-particle energies of 13, 15, and 15.2 MeV. Using method II of Litherland and Ferguson spin assignments or restrictions thereof could be made to the²⁷Al levels atE _x =5500 keV (I=11/2, 7/2), 6950 keV (I=11/2, 7/2), 7226 keV (I=9/2), 7286 keV (I=9/2–13/2), 7399 keV (I=11/2, 7/2) and 7443 keV (I=13/2, 9/2). Using the Doppler-shift attenuation method a lifetimeτ=20–50 fs was obtained for theE _x =7399 keV level and a limitτ<20 fs for the levels atE _x =7443, 7286, 7226, 6950, 6718, and 6287 keV, respectively. Further spin assignments in²⁷Al were obtained by a study of the²⁶Mg(p, γ) reaction at the E_p=2174 keV resonance. Fromγ-ray angular distributions the resonance spin was determined as I=9/2 (previous assignmentI=7/2) and the spin of theE _x =5959 keV level was determined asI=7/2. Tentative spin assignments were made to the levels atE _x =6537 keV (I=7/2) and 6718 keV (I=9/2). From the combined evidence of the²⁴Mg(α, p) and²⁶Mg(p, γ) reactions the spin of the 6287 keV level was found to beI=7/2. The results are compared with shell model calculations and the Nilsson model.     

Critical factors in obtaining meaningful fast MAS NMR spectra of non-integral spin quadrupolar nuclei. A review with particular emphasis on27Al MAS NMR of catalysts and minerals

In the last decade, magic angle spinning (MAS) NMR has become an extremely important method for studying the structure of inorganic solids. Advances in NMR technology have greatly aided in understanding the structure of catalysts, minerals, clays, ceramics, glasses, etc. Obtaining meaningful MAS spectra of spin-1/2 nuclei such as²⁹Si and³¹P is relatively straightforward and well understood. In contrast, obtaining meaningful MAS spectra is far from simple with non-integral spin quadrupolar nuclei such as¹¹B (I=3/2),¹⁷O (I=5/2),²³Na (I=3/2),²⁷Al (I=5/2),⁶⁹Ga (I=3/2), and⁷¹Ga (I=3/2)?to name some of the most commonly studied nuclei. Many additional factors have to be considered. This paper will deal with these factors and the utility of very fast MAS for studying non-integral spin quadrupolar nuclei in inorganic solids.     

Optical determination of the nuclear moments of137La

Using the reactor-produced lanthanum isotope ₅₇ ¹³⁷ La, the hyperfine structure (hfs) of the transition La I, 5d ² 6p z ⁴ G ₁₁ ^2/0 ?5d ² 6s a ⁴ F _9/2, λ=6250 Å and La I, 5d ² 6p z ² H ₁₁ ^2/0 ? 5d ² 6s a ²G_9/2, λ=6266 Å were measured by means of a Fabry-Pérot interferometer. The nuclear spin I (¹³⁷La)=7/2, already theoretically estimated by earlier authors, was confirmed. The nuclear magnetic dipole moment μ_I(¹³⁷La)=+ 2.690 (6) n.m. and the electric quadrupole momentQ(¹³⁷La)=+ 0.26 (8) · 10^?24 cm² were determined from the ratios of the hfs interaction constantsA andB of¹³⁷La and the natural¹³⁹La.     

Syntheses and structure characterization of inorganic/organic coordination polymers: Ag(dpa), Co(O3PH)(4,4′-bpy)(H2O), Zn(O3PH)(4,4′-bpy)0.5 and Mn[O2PH(C6H5)]2(4,4′-bpy) (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine)

Four novel coordination polymers: Ag(dpa) I, Co(O₃PH)(4,4′-bpy)(H₂O) II, Zn(O₃PH)(4,4′-bpy)_0.5 III and Mn[O₂PH(C₆H₅)]₂(4,4′-bpy) IV (dpa=2,2′-dipyridylamine; 4,4′-bpy=4,4′-bipyridine), were synthesized by microwave heating and characterized by X-ray crystallography. I crystallizes in monoclinic space group P21/n with a=11.576(2) Å, b=5.585(2) Å, c=15.243(4) Å, β=109.00(2)°, V=931.8(3) ų. II crystallizes in monoclinic Cc space group with a=22.477(7) Å, b=5.280(1) Å, c=10.404(4) Å, β=96.08(3)°, V=1227.8(7) ų. III crystallizes in monoclinic P21/c space group with a=9.758(2) Å, b=7.449(3) Å, c=10.277(2) Å, β=100.02(2)°, V=735.6(4) ų. IV crystallizes in monoclinic space group P2/c with a=10.174(1) Å, b=11.817(3) Å, c=18.784(4) Å, β=102.14(1)°, V=2207.8(8) ų. I consists of linear metal–metal chains wrapped by dpa ligands. II and III consist of two-dimensional M^II(O₃PH) inorganic sheets cross-linked by 4,4′-bpy ligands, while IV is formed by Mn[O₂PH(C₆H₅)]₂ sheets cross-linked by 4,4′-bpy ligands. I exhibits two-step thermal decomposition at ~200 and ~250°C, resulting in the reduction of Ag⁺ to Ag metal. II loses its coordination water at ~100°C, leaving vacant coordination sites at Co²⁺ ions, while the original framework remains intact. The removal of 4,4′-bpy in II–IV occurs at elevated temperatures above 250, 200 and 400°C respectively.     

The g-factor and the electric quadrupole moment of the 7/2+ isomer in125Xe

The time differential perturbed angular distribution method (PAD) was used to measure theg-factor and the electric quadrupole interaction in a Cd single crystal for thet _1/2=140 ns,I ^π=7/2⁺ isomer in¹²⁵Xe. Theg-factor isg=+0.264(10) and the quadrupole coupling constante ² Qq/h=122.1 (6) MHz at 552 K. The lifetime of theI ^π=11/2⁺ state was measured to beτ=11.3 (1.1) ps by the recoil distance method (RDM). From an analysis of the spectroscopic data using the triaxial-rotor-plus-particle (TRPP) model the quadrupole moment of the 7/2⁺ isomer is deduced to beQ=1.40 (15) b yielding an electric field gradient (efg)eq=3.6(4)·10¹⁷ V/cm² for XeCd.     

The low-lying states and configurations in138La

Tritons from the reaction¹³⁹La(d, t)¹³⁸La atE _d=16 MeV were analyzed at eleven reaction angles from 22 ° to 90 ° with a broad-range magnetic spectrograph. TheQ-value of the reaction is ?2522±5 keV. The nine lowest-lying states in¹³⁸La are interpreted in terms of the shell model configurations (πg _7/2)^?1 (vd _3/2)^?1, (πg _7/2)^?1 (vs _1/2)^?1 and (πg _7/2)^?2 (πd _5/2)^?1(vd _3/2)^?1. Seven levels in the energy range of 700–1300 keV are populated byl=5 transitions and are interpreted as coming from the (πg _7/2)^?1(vh _11/2)^?1 configuration. The ground state of¹³⁸La is shown to haveJ ^π=5⁺. Therefore, beta decay by unique second-forbidden transitions to the 2⁺ one-phonon states of¹³⁸Ce and¹³⁸Ba must be inferred in spite of unusually high logft values of 19.2 and 18.5, respectively.     

Hyperfine Interaction of 140Ce(←140La) in CaB6

A ¹⁴⁰La(I ^π=3⁻, T _1/2=40.3 h)-doped layer has been produced in CaB₆ by means of radioactive isotope (RI) beam technique: ¹⁴⁰Cs(I ^π=1⁻, T _1/2=63.7 s) was implanted into CaB₆ and the radioactive equilibrium of ¹⁴⁰Ba–¹⁴⁰La was achieved. The concentration of La in CaB₆ was La/Ca ∼0.001. Obtained TDPAC spectra of the 2083 keV level of ¹⁴⁰Ce (I ^π=4⁺, T _1/2=3.4 ns, μ=+4.35±0.10 μ _N ) followed by the β decay of ¹⁴⁰La showed the existence of hyperfine magnetic fields: B _hyp=−15.0±0.5 T and −1.00±0.15 T. This revised version was published online in September 2006 with corrections to the Cover Date.     

La NMR and As NQR study of the As-based filled skutterudite LaOs4As12

We report experimental results of nuclear magnetic resonance (NMR) at the La site and nuclear quadrupole resonance (NQR) at the As site in the normal state of the superconducting compound LaOs₄As₁₂. Measurements have been performed on powder sample obtained from high quality single crystals. The temperature dependences of the nuclear spin-lattice relaxation rates, 1/T₁, of ⁷⁵As and ¹³⁹La nuclei were measured. No scaling between them was found indicating a local character of relaxation processes. The relaxation of ⁷⁵As nuclei can consistently be understood in terms of antiferromagnetic spin fluctuations, as deduced from the T-dependence of (1/T₁T)=C/(T−θ)^1/2.     

Untersuchung der Struktur desu-u-Kerns142Pr durch (α, n γ)- und (p,n γ)-Reaktionen und Bestimmung von Matrixelementen der effektiven Proton-Neutron-Restwechselwirkung

The structure of the odd-odd nucleus¹⁴²Pr has been studied at the Erlangen Tandem Van de Graaff accelerator by using the nuclear reactions¹³⁹La(α, nγ) and¹⁴²Ce(p, n γ). Neutron-gamma and gamma-gamma coincidence measurements have been performed. In the frame work of the shell model the low lying states up to energies of 400 keV can be described as two mixed multiplettsC _1i ^I ¦j′ _p ,j _n ;I>+C _2i ^I ¦j″ _p ,'j _n ; I> (i=1, 2;j′ _p =2d5/2,j″ _p =1g 7/2^?1 andj _n =2f 7/2). From a fit of experimentally determinedγ-branching ratios to theoretical transition probabilities we have derived the amplitudes of the wavefunctions. From these wavefunctions and the energies of states and configurations in¹⁴²Pr we have obtained matrixelements of the effective residualp, n-interaction.     

Developments in quantum information processing by nuclear magnetic resonance: Use of quadrupolar and dipolar couplings

Use of dipolar and quadrupolar couplings for quantum information processing (QIP) by nuclear magnetic resonance (NMR) is described. In these cases, instead of the individual spins being qubits, the 2 ⁿ energy levels of the spin-system can be treated as an n-qubit system. It is demonstrated that QIP in such systems can be carried out using transition-selective pulses, in CH₃CN, ¹³CH₃CN, ⁷Li (I=3/2) and ¹³³Cs (I=7/2), oriented in liquid crystals yielding 2 and 3 qubit systems. Creation of pseudopure states, implementation of logic gates and arithmetic operations (half-adder and subtractor) have been carried out in these systems using transition-selective pulses.     

Optical properties of Er/Yb-codoped transparent PLZT ceramic

Optical absorption and emission spectra of Er³⁺/Yb³⁺ ions in PLZT (Pb_1−xLa_xZr_yTi_1−yO₃) ceramic have been studied. Based on the Judd—Ofelt (J-O) theory, the J-O intensity parameters were calculated to be Ω₂=2.021×10⁻²⁰ cm², Ω₄=0.423×10⁻²⁰ cm², Ω₆=0.051×10⁻²⁰ cm² from the absorption spectrum of Er³⁺/Yb³⁺-codoped PLZT. The J-O intensity parameters have been used to calculate the radiative lifetimes and the branching ratios for some excited ⁴I_13/2, ⁴I_11/2, ⁴I_9/2⁴F_9/2, and ⁴S_3/2 levels of Er³⁺ ion. The stimulated emission cross-section (8.24×10⁻²¹ cm²) was evaluated for the ⁴I_13/2→⁴I_15/2 transition of Er³⁺. The upconversion emissions at 538, 564, and 666 nm have been observed in Er³⁺/Yb³⁺-codoped PLZT by exciting at 980 nm, and their origins were identified and analyzed.     

Separation of isotropic chemical and second-order quadrupolar shifts by multiple-quantum double rotation NMR

Using a two-dimensional multiple-quantum (MQ) double rotation (DOR) experiment the contributions of the chemical shift and quadrupolar interaction to isotropic resonance shifts can be completely separated. Spectra were acquired using a three-pulse triple-quantum z-filtered pulse sequence and subsequently sheared along both the ν₁ and ν₂ dimensions. The application of this method is demonstrated for both crystalline (RbNO₃) and amorphous samples (vitreous B₂O₃). The existence of the two rubidium isotopes (⁸⁵Rb and ⁸⁷Rb) allows comparison of results for two nuclei with different spins (I = 3/2 and 5/2), as well as different dipole and quadrupole moments in a single chemical compound. Being only limited by homogeneous line broadening and sample crystallinity, linewidths of approximately 0.1 and 0.2 ppm can be measured for ⁸⁷Rb in the quadrupolar and chemical shift dimensions, enabling highly accurate determination of the isotropic chemical shift and the quadrupolar product, P_Q. For vitreous B₂O₃, the use of MQDOR allows the chemical shift and electric field gradient distributions to be directly determined—information that is difficult to obtain otherwise due to the presence of second-order quadrupolar broadening.     

Niederenergetische Gammalinien vom Neutroneneinfang in Lu 175 und Lu 176

The low energy gamma-rays from neutron-capture in Lu 175 and Lu 176 have been investigated by means of the bent crystal-spectrometer at the DR-3-reactor at Risø. From the transitions in Lu 177 3 rotational bands have been determined. The levels of the (404)K=7/2⁺ groundstate rotational band are: 121,62 keV (I=9/2), 268,79keV (I=11/2), 440,66 keV (I=13/2), 636,22 keV (I=15/2), 854,34 keV (I=17/2). The level-sequence of the (514)K=9/2^?-band is: 150,39 keV (I=9/2), 288,99 keV (I=11/2), 451,49 keV (I=13/2), 637,05 keV (I=15/2) and 844,88 keV (I=17/2). At 457,92 keV is the basis for the (402)K=5/2⁺-band the higher levels of which are 552,05 keV (I=7/2), 671,89 keV (I=9/2), 816,63 keV (I=11/2), 985,23 keV (I=13/2), 1176,73keV (I=15/2) and probably 1389,5 keV (I=17/2). The energies of the levels apart from the 1389 keV-level have an accuracy of 7×10^?5. The energy differences between the 3 bands agree very well with the values expected from the Bohr-Mottelson-formulaE=A·I(I+1)+B·I ²(I+1)². The calculated branching-ratios within the 3 bands are in fairly good agreement with the experimental values. Theg _K -factors have been determined for 2 bands: It was found that for the (514)-bandg _K =1,16±0,04 and for the (402)-bandg _K =1,33±0,07.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

Hyperfine structure measurements in the4 I 9/2 ground state of141Pr

Using the atomic beam magnetic resonance method, the five hyperfine structure separations in the 4f ³ 6s ^{2 4}I_9/2 ground state of ₅₉ ¹⁴¹ Pr have been measured. The results are:F F′ E _FF′ ^* /h (MHz) 7 6 6477.913423(17) 6 5 5556.359848 (6) 5 4 4633.023306 (2) 4 3 3708.201146 (5) 3 2 2782.190601(15) From these quantities, the multipole interaction constantsA _k,k=1, 2, 3, 4 between the nucleus and the electron shell have been calculated.A ₄ especially then served to give the following limit for the intrinsic hexadecapole moment: ¦Q ₄₀¦<0.4eb ². Furthermore, theg _J -factors of the⁴ I multiplet have been measured at magnetic fields of 300 Oe. The results are:g _J(⁴ I _9/2)=0.7310371(15)g _J(⁴ I _11/2)=0.9651476(20)g _J(⁴ I _13/2)=1.1063197(40)g _J(⁴ I _15/2)=1.197963 (30) Small corrections due to perturbations by neighbouring fine structure levels are included.     

Enhanced infrared to visible upconversion emission in Er3+ doped phosphate glass: Role of silver nanoparticles

Phosphate glasses with compositions (59.5–x)P₂O₅–MgO–xAgCl–0.5Er₂O₃ (0.0≤x≤1.5 mol%) containing fixed concentration of Er³⁺ ion with and without silver nanoparticles (NPs) are prepared using melt quenching technique. The amorphous nature of the glass is confirmed using the X-ray diffraction method. The homogeneous distribution of spherical Ag NPs (average size ～37 nm) in the glassy matrix is evidenced from the transmission electron microscopy (TEM) analyses. The UV–vis–NIR absorption spectra shows 10 bands corresponding to ⁴I_13/2, ⁴I_11/2, ⁴I_9/2, ⁴F_9/2, ⁴S_3/2, ²H_11/2, ⁴F_7/2, ⁴F_5/2, ²G_9/2, ⁴G_11/2 transitions in which the most intense bands are ²H_11/2 and ⁴G_11/2. The absorption spectrum of Er³⁺ ions free glass sample containing Ag NPs displays a prominent surface Plasmon resonance (SPR) band located at 528 nm. The infrared to visible frequency upconversion (UC) emission under 797 nm excitation shows two emission bands green (⁴S_3/2–⁴I_15/2) and red (⁴F_9/2–⁴I_15/2) centered at 540 nm and 634 nm, respectively, corresponding to Er³⁺ transitions. An enhancement in UC emission intensity of green band (⁴S_3/2–⁴I_15/2) is observed in the presence of silver NPs and the maximum enhancement occurred for 1.5 mol% AgCl. However, the enhancement of emission intensity of the red band (⁴F_9/2–⁴I_15/2) is smaller. The enhancement of UC emission is understood in terms of the intensified local field effect due to silver NPs.     

Nuclear structure effect on internal conversion ofl-forbidden transitions in139La,141Pr and203Tl

Accurate experimental internal conversion data have been used to study the effect of nuclear penetration in the case of thel-forbidden transitions in¹³⁹La (165.8 keV),¹⁴¹Pr (145.4 keV) and²⁰³Tl (279.2 keV). The nuclear penetration parameterλ and theE2/M 1 mixing ratioδ ² have been deduced by graphical analysis. Following results were obtained:λ=2.8±1.3,δ ² =(8.4 _?8.4 ^+14.0 )·10^?4 for¹³⁹La,λ=1.2±0.6,δ ²=(4.8±0.5)·10^?3 for¹⁴¹Pr, andλ=6.4±1.1,δ ²=1.36±0.12 for²⁰³Tl.     

The magnetic moment of the first excited state in138La

Theg-factor of the first excited state in the odd-odd nucleus¹³⁸La (E _x=73 keV,I _π,T _1/2=116 ns) was measured by the time-differential perturbed angular distribution (TDPAD) method. The result, corrected for Knight shift and diamagnetic shielding, isg=+0.962±0.016. This value can be fairly well reproduced using the additivity relation for magnetic moments, empirical values for the odd-proton and odd-neutrong-factors, and an experimentally deduced wave function for the 3⁺ state.     

Temperature and concentration dependence of spectroscopic properties of Nd-doped yttrium aluminum garnet crystal

The optical absorption spectra of yttrium aluminum garnet (YAG) crystals doped with Nd³⁺ ions with different concentrations (0.6 at%, 1.0 at%, 1.2 at%) at the temperature range from 300 K to 500 K have been measured. The calculated Judd–Ofelt (JO) parameters Ω_t (t=2, 4, 6) based on the spectra have been used to predict the radiative transition probabilities, branching ratios and radiative lifetimes of the transitions from ⁴F_3/2 level to the lower levels (⁴I_13/2, ⁴I_11/2, ⁴I_9/2) at each concentration and temperature. The three JO parameters Ω_t (t=2, 4, 6), according to the calculation, decrease with the increasing doped concentration at each temperature. The JO parameters Ω₂ and Ω₄ increase, while the parameter Ω₆ decreases with the increasing temperature at each concentration. The branching ratios and radiative transition probabilities of the transitions from the ⁴F_3/2 level to ⁴I_13/2 and ⁴I_11/2 levels decrease, while the transition from the ⁴F_3/2 level to ⁴I_9/2 level increases with the increasing temperature. The obtained results at each concentration and temperature are discussed.