Solvent dependent morphology and 59Co internal field NMR study of Co-aggregates synthesized by a wet chemical method.

Different shapes of Co-aggregates were synthesized via reduction of a Co salt (CoCl2·6H2O) by chemical precipitation using glycerol, ethylene glycol and ethanol as solvents. The effect of solvent on the morphology, fcc or hcp phase-content and the magnetic properties of the synthesized samples were investigated. The Co-aggregates synthesized using glycerol have a dense spherical shape and high saturation magnetization (MS), whereas ethylene glycol leads to formation of flower-shaped spherical aggregates through loose packing of smaller plate-like particles which have a moderate MS value. When ethanol was used as a solvent, a dendritic (leaf like)-shape of the aggregates with the lowest MS value was obtained. The formation of the obtained morphology of the aggregates was explained based on the size of the solvent molecule, the viscosity of the solvent and the number of polar groups (-OH) present in the solvent molecules. The magnetic domain state and domain wall dynamics of all the Co-samples were investigated using 59Co Internal Field Nuclear Magnetic Resonance (IFNMR) spectroscopy at RT and at 77 K. Through the IFNMR spectroscopy, the presence of gain boundaries, single domain particles and multi-domain particles/aggregates with domain walls associated with fcc and hcp phases were identified and quantified. We observed that the use of ethanol facilitates formation of a higher amount of hcp phase in the sample than the use of glycerol or ethylene glycol.

57Fe internal field nuclear magnetic resonance and Mössbauer spectroscopy study of Li-Zn ferrites.

We report the internal field nuclear magnetic resonance (IFNMR) and Mössbauer spectroscopy study of Li-Zn ferrites at RT. The results were supported by the IFNMR data measured at 77 K. As Zn concentration increases the IFNMR echo amplitude decreases and below certain Zn concentration no signal was detected. At RT the echo amplitude vanishes at a lower Zn concentration, whereas at 77 K, the echo amplitude does not vanish completely (except for pure Zn-ferrite). However, in Mössbauer spectroscopy at RT, we have observed magnetically ordered state of all the Li-Zn ferrite samples. This discrepancy could be related to the difference between the time scale of detection of the spins by Mössbauer spectroscopy (10-7-10-10 s) and NMR spectroscopy (10-6 s). Hence, sensitivity of zero-field NMR depends on the magnetic hyperfine field, temperature and abundance of the magnetic cations at the lattice of the spinel ferrites. We have demonstrated that the 'two-equal-pulses' sequence leads to higher echo signal than the spin echo pulse sequence due to the presence of distribution of internal magnetic fields throughout the material. We obtained a limiting value for the fraction of spins needed to produce an echo signal at a particular temperature and at a particular site of the Li-Zn ferrite spinels that can be sensitively detected by pulsed IFNMR technique.

Role of crystal field in mixed alkali metal effect: electron paramagnetic resonance study of mixed alkali metal oxyfluoro vanadate glasses.

The mixed alkali metal effect is a long-standing problem in glasses. Electron paramagnetic resonance (EPR) is used by several researchers to study the mixed alkali metal effect, but a detailed analysis of the nearest neighbor environment of the glass former using spin-Hamiltonian parameters was elusive. In this study we have prepared a series of vanadate glasses having general formula (mol %) 40 V2O5-30BaF2-(30 - x)LiF-xRbF with x = 5, 10, 15, 20, 25, and 30. Spin-Hamiltonian parameters of V(4+) ions were extracted by simulating and fitting to the experimental spectra using EasySpin. From the analysis of these parameters it is observed that the replacement of lithium ions by rubidium ions follows a "preferential substitution model". Using this proposed model, we were able to account for the observed variation in the ratio of the g parameter, which goes through a maximum. This reflects an asymmetric to symmetric changeover of the alkali metal ion environment around the vanadium site. Further, this model also accounts for the variation in oxidation state of vanadium ion, which was confirmed from the variation in signal intensity of EPR spectra.

Variations in magnetic properties of nanostructured nickel.

The magnetic properties of carbon nanotube encapsulated nickel nanowires (C.E. nanowires of diameter to approximately 10 nm), and its comparison to other forms of Ni are carried out in this work. The saturation magnetization (Ms) and coercivity (Hc) for C.E. nanowires are 1.0 emu/g and 230 Oe. The temperature dependence of coercivity follows T0.77 dependence indicating a superparamagnetic behavior. The field-cooled and zero-field-cooled plots indicate that the blocking temperature (T(B)) to approximately 300 K. These altered magnetic properties of C.E. nanowires are mainly due to the nanoscale confinement effect from carbon nanotube encapsulation. The shape and magnetic environment enhance the total magnetic anisotropy of C.E. nanowires by a factor of four.

35Cl NQR frequency and spin lattice relaxation time in 3,4-dichlorophenol as a function of pressure and temperature.

The pressure dependences of (35)Cl nuclear quadrupole resonance (NQR) frequency, temperature and pressure variation of spin lattice relaxation time (T(1)) were investigated in 3,4-dichlorophenol. T(1) was measured in the temperature range 77-300 K. Furthermore, the NQR frequency and T(1) for these compounds were measured as a function of pressure up to 5 kbar at 300 K. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities W(1) and W(2) for the Δm = ±1 and Δm = ±2 transitions were also obtained. A nonlinear variation of NQR frequency with pressure has been observed and the pressure coefficients were observed to be positive. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. An attempt is made to compare the torsional frequencies evaluated from NQR data with those obtained by IR spectra. On selecting the appropriate mode from IR spectra, a good agreement with torsional frequency obtained from NQR data is observed. The previously mentioned approach is a good illustration of the supplementary nature of the data from IR studies, in relation to NQR studies of compounds in solid state.

Correlated conformation and charge transport in multiwall carbon nanotube-conducting polymer nanocomposites.

The strikingly different charge transport behaviours in nanocomposites of multiwall carbon nanotubes (MWNTs) and conducting polymer polyethylenedioxythiophene-polystyrene-sulfonic-acid (PEDOT-PSS) at low temperatures are explained by probing their conformational properties using small-angle x-ray scattering (SAXS). The SAXS studies indicate the assembly of elongated PEDOT-PSS globules on the walls of nanotubes, coating them partially, thereby limiting the interaction between the nanotubes in the polymer matrix. This results in a charge transport governed mainly by small polarons in the conducting polymer despite the presence of metallic MWNTs. At T > 4 K, hopping of the charge carriers following one-dimensional variable range hopping is evident which also gives rise to a positive magnetoresistance (MR) with an enhanced localization length (∼5 nm) due to the presence of MWNTs. However, at T < 4 K, the observation of an unconventional positive temperature coefficient of resistivity is attributed to small polaron tunnelling. The exceptionally large negative MR observed in this temperature regime is conjectured to be due to the presence of quasi-1D MWNTs that can aid in lowering the tunnelling barrier across the nanotube-polymer boundary resulting in large delocalization.

Temperature- and pressure-dependent study of 35Cl NQR frequency and spin lattice relaxation time in 2,3-dichloroanisole.

The temperature and pressure dependence of (35)Cl NQR frequency and spin lattice relaxation time (T(1)) were investigated in 2,3-dichloroanisole. Two NQR signals were observed throughout the temperature and pressure range studied. T(1) were measured in the temperature range from 77 to 300 K and from atmospheric pressure to 5 kbar. Relaxation was found to be due to the torsional motion of the molecule and also reorientation of motion of the CH(3) group. T(1) versus temperature data were analyzed on the basis of Woessner and Gutowsky model, and the activation energy for the reorientation of the CH(3) group was estimated. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities were also obtained. NQR frequency shows a nonlinear behavior with pressure, indicating both dynamic and static effects of pressure. The pressure coefficients were observed to be positive for both the lines. A thermodynamic analysis of the data was carried out to determine the constant volume temperature coefficients of the NQR frequency. The variation of spin lattice time with pressure was very small, showing that the relaxation is mainly due to the torsional motions of the molecules.

Study of molecular dynamics and cross relaxation in tetramethylammonium hexafluorophosphate (CH(3))(4)NPF(6) by (1)H and (19)F NMR.

(CH(3))(4)NPF(6) is studied by NMR measurements to understand the internal motions and cross relaxation mechanism between the heterogeneous nuclei. The spin lattice relaxation times (T(1)) are measured for (1)H and (19)F nuclei, at three (11.4, 16.1 and 21.34 MHz) Larmor frequencies in the temperature range 350-50K and (1)H NMR second moment measurements at 7 MHz in the temperature range 300-100K employing home made pulsed and wide-line NMR spectrometers. (1)H NMR results are attributed to the simultaneous reorientations of both methyl and tetramethylammonium groups and motional parameters are evaluated. (19)F NMR results are attributed to cross relaxation between proton and fluorine and motional parameters for the PF(6) group reorientation are evaluated.

Pressure and temperature dependence of the chlorine NQR in caesium and sodium chlorates.

The (35)Cl nuclear quadrupole resonance (NQR) frequencies (nu(Q)) in caesium and sodium chlorates were measured as a function of temperature, from 77 to 300 K at different pressures up to 5.1 kbar, and the data were analysed to estimate the volume dependence of the electric field gradient (EFG), torsional frequency and also the contributions to the NQR frequency from static and dynamic effects. The variation of spin-lattice relaxation time with pressure at different temperatures was studied in the case of sodium chlorate and at room temperature in case of caesium chlorate. The pressure dependence of the spin-lattice relaxation time (T(1)) suggests that the relaxation is mainly due to the torsional motions.

1H NMR study of internal motions and quantum rotational tunneling in (CH3)4NGeCl3.

(CH3)4NGeCl3 is prepared, characterized and studied using 1H NMR spin lattice relaxation time and second moment to understand the internal motions and quantum rotational tunneling. Proton second moment is measured at 7 MHz as function of temperature in the range 300-77 K and spin lattice relaxation time (T1) is measured at two Larmor frequencies, as a function of temperature in the range 270-17 K employing a homemade wide-line/pulsed NMR spectrometers. T1 data are analyzed in two temperature regions using relevant theoretical models. The relaxation in the higher temperatures (270-115 K) is attributed to the hindered reorientations of symmetric groups (CH3 and (CH3)4N). Broad asymmetric T1 minima observed below 115 K down to 17 K are attributed to quantum rotational tunneling of the inequivalent methyl groups.

(1)H-NMR and charge transport in metallic polypyrrole at ultra-low temperatures and high magnetic fields.

The temperature dependence of conductivity, proton spin relaxation time (T(1)) and magnetoconductance (MC) in metallic polypyrrole (PPy) doped with PF(6)(-) have been carried out at mK temperatures and high magnetic fields. At T<1 K both electron-electron interaction (EEI) and hopping contributes to conductivity. The temperature dependence of a proton T(1) is classified in three regimes: (a) for T<6 K-relaxation mechanism follows a modified Korringa relation due to EEI and disorder, (b) for 6 K50 K-relaxation is due to the dipolar interaction modulated by the reorientation of the symmetric PF(6) groups following the Bloembergen, Purcell and Pound (BPP) model. The data analysis shows that the Korringa ratio is enhanced by an order of magnitude. The positive and negative MC at T<250 mK is due to the contributions from weak localization and Coulomb-correlated hopping transport, respectively. The role of EEI is observed to be consistent in conductivity, T(1) and MC data, especially at T<1 K.

Disorder in condensed matter systems: proton spin lattice relaxation study of the mixed systems of betaine phosphate and glycine phosphite, BPxGPI(1-x).

Proton NMR relaxation measurements have been carried out in the mixed system of antiferroelectric (AFE) betaine phosphate (BP) and ferroelectric (FE) glycine phosphite (GPI), BPxGPI(1-x), at 11.4 and 23.3 MHz from 300 to 100 K for x=0.3, 0.4, 0.5, 0.6, 0.7 and 0.8. The temperature dependence of spin lattice relaxation (SLR) time follows the BPP model in the parent compounds, while the Larmor frequency dependence of T1 in the mixed system is rather unusual. The T1 curve exhibits different slopes for the low-temperature wings at the two frequencies, which is a clear experimental evidence of the presence of different methyl groups with different activation energies (Ea), indicating disorder. For x=0.3 and 0.4, biexponential recovery of magnetization has been observed below 190 K, showing that the degree of disorder varies with the concentration. The temperature dependence of relaxation time data has been interpreted in terms of NH3, trimethyl ammonium and methyl group reorientations.

Study of molecular reorientation and quantum rotational tunneling in tetramethylammonium selenate by 1H NMR.

1H NMR spin-lattice relaxation time measurements have been carried out in [(CH3)4N]2SeO4 in the temperature range 389-6.6 K to understand the possible phase transitions, internal motions and quantum rotational tunneling. A broad T1 minimum observed around 280 K is attributed to the simultaneous motions of CH3 and (CH3)4N groups. Magnetization recovery is found to be stretched exponential below 72 K with varying stretched exponent. Low-temperature T1 behavior is interpreted in terms of methyl groups undergoing quantum rotational tunneling.

Dependence of (35)Cl NQR on hydrogen bonding and temperature in dichlorophenol-aniline charge transfer complexes.

The hydrogen-bonded charge transfer complexes of aniline with pi-acceptors (or proton donors) such as 2,5-, 2,6-, 3,4- and 3,5-dichlorophenol were prepared. The (35)Cl nuclear quadrupole resonance (NQR) frequencies of these charge transfer complexes in the temperature range 77-300 K were measured to ascertain the existence or otherwise of a phase transition upon complex formation. Further, the NQR frequency and asymmetry parameter of the electric field gradient at the site of quadrupole nucleus were used to estimate the chemical bond parameters, namely ionic bond, double bond character of the carbon-chlorine(C--Cl) bond and the percentage charge transfer between the donor-acceptor components in charge transfer complexes. The effect of hydrogen bonding and temperature on the charge transfer process is analysed.

Solution combustion derived nanocrystalline Zn(2)SiO(4):Mn phosphors: a spectroscopic view.

Manganese doped nanocrystalline willemite powder phosphors Zn(2-x)Mn(x)SiO(4) (0.1(6)A(1) ground state. The mechanism involved in the generation of a green emission has been explained in detail. The effect of Mn content on luminescence has also been studied.