Determination of titanium NMR parameters of ATiO3 compounds: correlations with structural distortion

Solid state ^47,49Ti NMR spectra have been obtained for a number of perovskite and ilmenite ATiO₃ compounds. The ⁴⁹Ti quadrupole coupling constant varies from 2.75 MHz (CaTiO₃) to 15.5 MHz (MgTiO₃) and the electric field gradient at the titanium site was found to correlate well with the shear strain, independent of structure. The chemical shift in the perovskite structures varies by 160 ppm and correlates well with the mean Ti–O distance. The ²⁵Mg and ¹¹³Cd NMR parameters are also reported for the relevant compounds.     

Mössbauer Study of the Ni/Ca0.8Sr0.2Ti1−x Fe x O3−α Catalyst System for Partial Oxidation of Methane to Synthesis Gas

The Ni/Ca_0.8Sr_0.2TiO₃ catalyst system prepared by the citrate method shows high activity in partial oxidation of methane to synthesis gas. It is assumed that the interaction of Ni with the perovskite lattice may be responsible for the increased catalytic activity. 1% ⁵⁷Fe dopant substituted for Ti was used in order to see if the presence of Ni has any perturbation effect on the structure of the perovskite. One may expect systematic changes in the Mössbauer parameters of the substitutional Fe impurity as a function of the NiO content if the bulk properties of the perovskite are affected. Samples with different Ni/Ca_0.8Sr_0.2Ti_0.99 ⁵⁷Fe_0.01O_3– ratios from 0:1 to 1:1, and others having Fe substitutions for Ti up to 30%, all prepared by the citrate method, have been investigated. The Mössbauer spectra contained doublets of paramagnetic Fe³⁺ and Fe⁴⁺ species as well as paramagnetically relaxed Fe³⁺. These species were assigned to the bulk perovskite, the perovskite surface and the NiO/perovskite interface. The perturbation of the perovskite structure by Ni could not be verified.     

Structure and refractive index dispersive behavior of potassium niobate tantalate films prepared by pulsed laser deposition

Pure perovskite phase and crack-free KTa_0.5Nb_0.5O₃ thin films were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. The structure and orientation were analyzed by X-ray diffraction. The optical properties were investigated by an ellipsometer. The relationship between the refractive index dispersive behavior and internal structure was analyzed by Sellmeier dispersion model and single electronic oscillator approximation. The parameters of room temperature monomial Sellmeier oscillator were calculated. And the refractive index dispersive parameter E₀/S₀ of KTa_0.5Nb_0.5O₃ thin films on Pt/Ti/SiO₂/Si substrates is (6.72 ± 0.04) × 10⁻¹⁴ eV m², which is consistent with those of KTN crystals and compounds with ABO₃ perovskite type structure.     

Hyperfine field and electric quadrupole interaction of51V in YFe2 and HoFe2

Spin echo measurements were made on Y(Fe_0.99V_0.01)₂, (Y_0.97Ho_0.03) (Fe_0.99V_0.01)₂ and Ho(Fe_0.96 V_0.04)₂ compounds. The addition of Ho to YFe₂ causes a spin reorientation from <111> to <100> but this is not reflected in the⁸⁹Y or⁵¹V hyperfine fields. A well resolved⁵¹V NMR line was observed at 51.5 MHz and 60.0 MHz respectively for Y and Ho Laves compounds but with no evidence of quadrupole satellites. Small quadrupole splittings ¦2P_t¦ = 171 ±5 kHz and 178 ±5 kHz respectively for Y and Ho compounds were deduced from the oscillatory decay of the⁵¹V spin echo after a two pulse sequence.On leave from Department of Physics, University College, The University of New South Wales, Australian Defence Force Academy, Campbell, ACT, Australia.     

Microscopic magnetic properties of (V1−xTix)2O3 near the phase boundary of the metal–insulator transition

Magnetic susceptibility (χ) and ⁵¹V NMR have been measured in (V_1−xTi_x)₂O₃ near the phase boundary of the metal–insulator transition. It is established that the transition from antiferromagnetic insulating (AFI) to antiferromagnetic metallic phases near x_c≈0.05 is not quantum critical, but is discontinuous with a jump of the transition temperature. In the AFI phase at 4.2 K, we observed the satellite in the zero-field ⁵¹V NMR spectrum around 181 MHz in addition to the ‘host’ resonance around 203 MHz. The satellite is also observable in the paramagnetic metallic phase of the x=0.055 sample. We associated the satellite with the V sites near Ti, which are in the V³⁺-like oxidation state, but has different temperature dependence of the NMR shift from that of the host V site. The host d-spin susceptibility for x=0.055 decreases below ∼60 K, but remains finite in the low-temperature limit.     

Effect of the“3-d” band filling on the structural,electronic, magnetic and optical properties of TMScO3 perovskite

The effect of filling of 3-d orbitals on structural, electronic, magnetic and optical properties of TMScO₃ perovskite, where TM is 3-d series from Ti to Zn, is studied through the Density Functional Theory (DFT) utilizing full potential linearized augmented plane wave (FP-LAPW) method using mBJ approximation.Filling the outer “d” shells of TM atoms in TMScO₃ changes the compounds behavior as TM atoms changes from Ti to Zn properties of materials. The total magnetic moment (M_t) increases as the 3-d orbitals filling increases, its maximum value occurs for MnScO₃ perovskite as Mn is in the middle of the 3-d transition series. Beyond this M_t tends to decrease with a minimum value for ZnScO₃. All compounds show half metallicity behavior (except for TiScO₃ which shows metallic behavior). The rest of properties (lattice constant, energy band gaps E_g and optical properties) are also affected by 3d-shell filling.     

Synthesis of nano-sized polycrystalline PZT powders using molecular building blocks by designed chemical route

Polycrystalline perovskite Pb(Zr _x Ti O₃ (PZT) powders in the form of particles with sizes in the range 2∼ ∼10 nm were obtained by hydrolysis of a mixed metal alkoxide precursor. The mixed metal alkoxide precursor was synthesized by refluxing Pb(OAc)₂, Zr(O– ⁿ Bu)₄ and Ti(O–ⁱPr)₄ in anhydrous ethanol. After it was hydrolyzed in a solution with a pH of 3 and dried at 423 K, nano-sized polycrystalline perovskite PZT was obtained. This temperature of formation of the PZT perovskite phase is noticeably lower than those reported elsewhere. The sizes of the freshly dried polycrystalline perovskite PZT particles are within the range of 2–5 nm.     

NMR studies of U0.2Y0.8Pd3 and YPd3 at low temperatures

We report results of ⁸⁹Y-NMR measurements on U_0.2Y_0.8Pd₃ as well as YPd₃, performed at frequencies between 9 and 16MHz and at temperatures between 0.25 and 2 K. In this temperature range the average Knight shift is +0.5%, temperature-independent and the same for both materials. Also the NMR linewidth for both compounds was found to be temperature and field independent but one order of magnitude larger for U_0.2Y_0.8Pd₃ than for YPd₃. For U_0.2Y_0.8Pd₃ our results indicate a distribution of internal static fields at the Y sites and a small temperature-dependent enhancement of the spin-lattice relaxation rate T ₁ ^?1 with respect to YPd₃. The NMR spectra are consistent with the presence of very small frozen U moments, but the temperature dependence of the spin-lattice relaxation rate indicates a more complicated situation. In particular (T₁T)^?1 shows an anomalous temperature dependence.     

X-ray photoelectron spectroscopic study of perovskite titanates and related compounds: An example of the effect of polarization on chemical shifts

The differences of the binding energy of the Ti 2P_{$\text{3}\text{2}$} electrons obtained by X-ray photoelectron spectroscopy in various perovskite type titanates and related compounds have been studied. The titanium compounds studied were titanium dioxide (anatase and rutile), calcium titanate, strontium titanate, lead titanate and barium titanate. The oxidation number of the titanium ion for all of these compounds is formally 4+. However, the X-ray photoelectron spectra show small shifts in the Ti 2p_{$\text{3}\text{2}$} binding energy as the cation is varied. An analysis of data led to the conclusion that this shift is mainly due to differences in polarization energy between these compounds.     

Electronic properties of Pb(ZrTi)O3 solid solutions

The theoretical backgrounds and some experimental data on the electronic properties of polycrystalline Pb(Zr, Ti)O₃ solid solutions are summarized. These substances occur in the perovskite structure, and so their electronic band structure is presumed to be analogous to other perovskite compounds. Their forbidden gap energy has been determined to be about 3.30–3.56 eV on the basis of optical, photoacoustical, and photoelectrical measurements. Many local levels and traps exist in the forbidden gap because of the polycrystalline character and heterovalent doping. Their actual configurations and states strongly influence the optical, photoelectrical, piezoelectrical, and other physical properties of Pb(Zr, Ti)O₃ solid solutions.     

NMR Studies of Hindered Rotation. The Diels-Alder Adduct of N-n-Butylmaleimide With Phencyclone: Restricted Motion of Bridgehead Phenyls

The Diels-Alder adduct of phencyclone and N-n-butylmaleimide has been prepared, and NMR studies have been carried out in CDCl₃ solution at ambient temperatures by one-and two-dimensional ¹H NMR (300 MHz) and ¹³C NMR (75 MHz) techniques. The resulting spectra appear to be consistent with slow rotation about the hindered C(sp²)-C(sp³) bonds to the bridgehead unsubstituted phenyls, i.e., slow exchange limit (SEL) spectra. Full rigorous ¹H spectral assignments have been made via high-resolution COSY experiments. The number of signals in the ¹³C NMR aryl region were also consistent with hindered phenyl rotations; preliminary ¹³C assignments are given. Striking evidence for magnetic anisotropic effects due to the phenanthrene moiety, bridging ketone carbonyl, and bridgehead phenyls are discussed, supporting endo stereochemical assignment of the adduct.     

Assignment of 13C Resonances in the Phencyclone-Norbornadiene Adduct Via 2D NMR. 13C Evidence for Hindered Rotation of Unsubstituted Bridgehead Phenyl Rings

¹³C NMR chemical shift assignments were obtained for the Diels-Alder adduct of phencyclone with norbornadiene in CD₂Cl₂ and in CDCl₃ solution. The ¹³C spectrum at 50.3 MHz, as well as the ¹H spectrum at 200.1 MHz, show evidence for hindered rotation of the two unsubstituted bridgehead phenyl rings of the adduct at ambient temperatures. In CD₂Cl₂ solution, all 19 of the unique ¹³C nuclei of this molecule give rise to individual ¹³C resonances. The ¹H assignments which were made earlier, together with one-bond and long-range 2D heteronuclear correlation experiments, allowed the assignment of all ¹³C chemical shifts in the molecule.     

7Li NMR analysis on perovskite structured Li0.15La0.28TaO3

The nanocrystalline perovskite material Li_0.15La_0.28TaO₃ has been synthesized by alkoxide-free Pechini type sol gel method. ⁷Li NMR measurements were carried out using a Bruker Avance 300 spectrometer at 116 MHz over the temperature range 150 to 400 K. Longitudinal spin-lattice relaxation times (T₁) measured by saturation recovery and longitudinal relaxation times in the rotating frame (T_1ρ) measured using the pulse sequence (π/2–spin lock τ acquisition) with lock radio-frequency field υ = 62.5 kHz and the T₂ relaxation time measured by Hahn echo are presented. The static Hahn-echo spectra show two different lithium sites in this perovskite oxide. Further, the relaxation measurements T₁ and T_1ρ show two different types of lithium cations with fast and slow dynamics.     

Spin echo and nuclear orientation study of metallic glasses

Hyperfine fields on Co nuclei in amorphous as-quenched and heat-treated Co₇₅Fe₅B₂₀ samples were studied by conventional NMR and by very low temperature nuclear orientation techniques. The Co spin echo measurement at 1.4 K yielded broad spectra between 130 – 260 MHz, with narrow maxima at 145.5 MHz and 155.1 MHz for as-quenched sample and with a broad maximum at 227 MHz for heat-treated sample well below the recrystallization point. The⁶⁰Co nuclear orientation measurements gave the mean value of hyperfine field B_hf15 T nearly independent of the sample heat-treatment. The spin-lattice relaxation was studied by pulse NMR and also by nuclear orientation thermal cycling technique.     

Experimental evidences of clusters with different short range order in amorphous alloys

⁵⁶Fe,⁵⁷Fe,¹⁰B and¹¹B isotopes were used for binary alloys. The signals of B (40,5 MHz) and Fe (43 MHz) from α-Fe in binary Fe−B crystalline and amorphous alloys were found besides the signals of these nuclei in t-and o-phase or clusters like these phases. The NMR on (51)V impurity nuclei in Fe−B alloys was used as well. Only amorphous Fe-(^<15 at.%B) alloys had the clusters with o-, t-Fe₃B and α-Fe short range order.     

The effects of substrate temperatures on the electrical properties of CaZrO3 thin films prepared by RF magnetron sputtering

The radio frequency magnetron sputtering technology (RFMS) was employed to deposit perovskite structure orthogonal phase CaZrO₃ thin films on Pt/Ti/SiO₂/Si substrates. The effects of substrate temperatures on structure and electrical properties of these films were investigated in detail. The CaZrO₃ thin films were systematically characterized by means of X-ray diffraction (XRD), Scanning electron microscope (SEM), Multi-frequency LCR meter (HP4294A) and Radiant Precision Workstation to study the phase structure, cross-section morphology, dielectric and ferroelectric properties at different substrate temperatures. The result indicates that these films can withstand 80 V DC Bias voltage and have excellent stability of frequency, voltage and temperature. The CaZrO₃ thin film prepared at 550 °C turned out to be mainly orthorhombic CaZrO₃ phase with high permittivity, low dielectric loss, extremely low leakage current (at 1 MHz, the dielectric constant is 39.42, the dielectric loss is 0.00455, the quality factor is 220 and the leakage current density is 9.11 × 10⁻⁷A/cm² at 80 V applied voltage.). This work demonstrates that higher substrate temperature can boost the formation of orthorhombic CaZrO₃ phase and the CaZrO₃ thin film prepared by RF magnetron sputtering is a very promising paraelectric material in the application of thin film capacitor.     

NMR Studies of Drugs. Methaqualone. Approaches to Rigorous 1H and 13C Assignments with Applications of Achiral and Chiral Shift Reagents

The ¹H and ¹³C NMR spectra of methaqualone, 1, have been extensively studied using one and two-dimensional techniques. These 300 MHz ¹H and 75 MHz ¹³C studies have allowed rigorous assignments to be made for the methyl groups and the quinazolinone nucleus. The 60 MHz ¹H spectra for 1 in CDCl₃ have been examined with     

NMR Studies of Hindered Rotation. The Diels-Alder Adduct of Phencyclone with N-n-Propylmaleimide: Restricted Motion of Bridgehead Phenyls

The Diels-Alder adduct of phencyclone and N-n-propylmaleimide has been studied in CDCl₃ solution at ambient temperatures by one-and two-dimensional ¹H NMR (300 MHz) and ¹³C NMR (75 MHz) techniques. Clear evidence is presented from slow exchange limit (SEL) spectra for hindered rotation of the bridgehead phenyls in the adduct. Full ¹H spectral assignments have been made via selective homonuclear decoupling and high resolution COSY experiments. The number of signals in the aryl region of ¹³C NMR spectra also indicated slow rotation about the C(sp²)-C(sp³) bond to the unsubstantiated bridgehead phenyls. Striking evidence of magnetic anisotropic effects, seen from ¹H NMR, permits stereochemical assignment of the adduct as endo.     

An injection-seeded high-repetition rate Ti:Sapphire laser for high-resolution spectroscopy and trace analysis of rare isotopes

An injection-seeded high-repetition rate (～10 kHz) Ti:sapphire laser with a spectral bandwidth of ～20 MHz and an average output power of above 1.5 W has been developed. We report on its demonstration and characteristics with respect to the spectral, temporal, and spatial properties as well as the output energy. In crossed-beam resonance ionization on a well-collimated thermal atomic beam, the ～200 MHz hyperfine structure of the D₂ transition at 308 nm of ²⁷Al has been well resolved. Applications of the system in the field of insource laser spectroscopy for on-line produced short-lived radioactive isotopes as well as for selective-trace isotope determination are discussed.     

NMR and Mössbauer study of multiferroic BiFeO<Subscript>3</Subscript>

Pulse nuclear magnetic resonance (NMR) was applied in studying the effect of ⁵⁷Fe isotope content in multiferroic BiFeO₃ on the shape of NMR spectra at 4.2 K. Strong dependences of the NMR line shape on the isotope content and transverse relaxation time were found. Consideration of these effects on NMR line shape shows that there is an undisturbed (with no anharmonicity effect) space spin-modulated structure of the cycloid type in BiFeO₃. The Mössbauer effect was also used to investigate the perovskite BiFeO₃ at 650, 295, and 87 K. Experimental spectra allowed us to obtain the distribution of hyperfine fields, which was found to be consistent with studies of the NMR line shape. The local electronic and magnetic states of the iron ion were measured.