Spin-lattice Relaxation Processes Research Articles

1H Spin-Lattice Relaxation Processes in Solutions of H2N-Fe3O4 Nanoparticles: Insights from NMR Relaxometry.

1H spin-lattice relaxation experiments have been performed for water and glycerol/water solutions of H2N-Fe3O4 superparamagnetic nanoparticles (NPs) of about 7 nm diameter. The experiments encompass a broad frequency range covering 3 orders of magnitude, from 10 kHz to 10 MHz (referring to 1H resonance frequency), and have been performed in the temperature range from 298 to 313 K, varying the concentration of the superparamagnetic species. This extensive dataset has been used for twofold purposes. The first one is to serve as a challenge for thorough tests of theoretical models describing nuclear relaxation in solutions of superparamagnetic NPs, depending on their magnetic properties and dynamics of the solvent molecules. The challenge is posed by the wish to reproduce the data in a broad range of magnetic fields (not only at high fields) and by the need to explain the differences in the relaxation scenarios for water and glycerol/water solutions by varying only the solvent parameters. The second purpose is to get insights into the magnetic properties (electronic relaxation properties) of the nanoparticles due to their high applicational potential.

Application of electron paramagnetic resonance spectroscopy to examine free radicals formed in indapamide and torasemide storage under UV irradiation and at the higher temperatures which appear under light exposition

Free radical formation in two diuretics: indapamide and torasemide was examined during UV irradiation and storage at higher temperatures using X-band (9.3 GHz) electron paramagnetic resonance spectroscopy (EPR). The aim of this study was to investigate the possibility of storing indapamide and torasemide under UV irradiation and at higher temperatures, which may occur during exposure to light. The diuretic samples were exposed to UVA irradiation for 15, 30 and 45 minutes, and stored at temperatures of 40 °C and 50 °C by 30 minutes. The EPR spectra were analyzed to determine the amplitudes (A), linewidths (ΔBpp), and integral intensities (I) and g factors. The concentrations of free radical (N) in the diuretic samples were also determined. The influence of microwave power on amplitudes, linewidths and the asymmetry parameter were evaluated. The result showed that the tested indapamide and torasemide samples exhibited high free radical concentrations in the range of 1018-1019 spin/g after UV irradiation and heat treatment. Therefore, due to the significant free radical formation indapamide and torasemide should not be stored under UV light and at temperatures of 40 °C and 50 °C. The complex character of free radical systems in the diuretic samples was proved as evidenced by the changes of the asymmetry parameters of the EPR lines with increasing microwave power. Fast spin-lattice relaxation processes were observed in all tested diuretic samples, regardless of the storage conditions. Electron paramagnetic resonance spectroscopy is proposed as a useful method in pharmacy to determine the appropriate storage conditions for diuretics.

Lattice-driven femtosecond magnon dynamics in α−MnTe

The light-induced femtosecond dynamics of the sublattice magnetizations in the antiferromagnetically ordered phase of the semiconductor $\alpha$-MnTe is investigated theoretically as function of an external driving field. The electromagnetic field is coupled to optical modes and the concomitant atomic displacements modulate the Heisenberg exchange couplings. We derive the equations of motion for the time-dependent sublattice magnetization in spin wave theory and analyze the contributions from the driven magnon modes. The antiferromagnetic order parameter exhibits coherent longitudinal oscillations determined by the external driving frequency which decay due to dephasing. Including a phenomenological dissipative term to mimic spin-lattice relaxation processes leads to relaxation back to thermal equilibrium. We provide approximate analytic solutions of the resulting differential equations which allow us to understand the effect of the driving light pulse on the amplitude, frequency, and lifetime of the coherent spin dynamics.

Charge Order and Fluctuations in Bi2Sr2−xLaxCuO6+δRevealed by63,65Cu-Nuclear Magnetic Resonance

The discovery of a magnetic-field-induced charge-density-wave (CDW) order in the pseudogap state via nuclear magnetic resonance (NMR) studies has highlighted the importance of “charge” in the physics of high transition-temperature (Tc) superconductivity in copper oxides (cuprates). Herein, after briefly reviewing the progress achieved in the last few years, we report new results of 63,65Cu-NMR measurements on the CDW order and its fluctuation in the single-layered cuprate Bi2Sr2−xLaxCuO6+δ. The NMR spectrum under both in- and out-of-plane magnetic fields above H = 10 T indicates that the CDW replaces the antiferromagnetic order before superconductivity appears, but disappears before superconductivity is optimized. We found that the CDW onset temperature TCDW scales with the pseudogap temperature T*. Comparison between 63Cu and 65Cu NMR indicates that the spin–lattice relaxation process is dominated by charge fluctuations in the doping regions where the CDW appears as well as at the pseudogap end point (T* = 0). These results suggest that charge orders and fluctuations exist in multiple doping regions and over a quite wide temperature range.

Probing Vibrational Symmetry Effects and Nuclear Spin Economy Principles in Molecular Spin Qubits.

The selection of molecular spin qubits with a long coherence time, Tm, is a central task for implementing molecule-based quantum technologies. Even if a sufficiently long Tm can be achieved through an efficient synthetic strategy and ad hoc experimental measurement procedures, many factors contributing to the loss of coherence still need to be thoroughly investigated and understood. Vibrational properties and nuclear spins of hydrogens are two of them. The former plays a paramount role, but a detailed theoretical investigation aimed at studying their effects on the spin dynamics of molecular complexes such as the benchmark phthalocyanine (Pc) is still missing, whereas the effect of the latter deserves to be examined in detail for such a class of compounds. In this work, we adopted a combined theoretical and experimental approach to investigate the relaxation properties of classical [Cu(Pc)] and a CuII complex based on the ligand tetrakis(thiadiazole)porphyrazine (H2TTDPz), characterized by a hydrogen-free molecular structure. Systematic calculations of molecular vibrations exemplify the effect of normal modes on the spin–lattice relaxation process, unveiling a different contribution to T1 depending on the symmetry of normal modes. Moreover, we observed that an appreciable Tm enhancement could be achieved by removing hydrogens from the ligand.

Magnetic field tuning of low-energy spin dynamics in the single-atomic magnet Li2(Li1−xFex)N

We present a systematic ${}^{57}\mathrm{Fe}$ M\"ossbauer study on highly diluted Fe centers in ${\mathrm{Li}}_{2}({\mathrm{Li}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{x})\mathrm{N}$ single crystals as a function of temperature and magnetic field applied transverse and longitudinal with respect to the single-ion anisotropy axis. Below 30 K, the Fe centers exhibit a giant magnetic hyperfine field of ${\overline{B}}_{A}=70.25(2)\phantom{\rule{4pt}{0ex}}\mathrm{T}$ parallel to the axis of strongest electric field gradient ${\overline{V}}_{zz}=\ensuremath{-}154.0(1)\phantom{\rule{4pt}{0ex}}\mathrm{V}/{\AA{}}^{2}$. Fluctuations of the magnetic hyperfine field are observed between 50 and 300 K and described by the Blume two-level relaxation model. From the temperature dependence of the fluctuation rate, an Orbach spin-lattice relaxation process is deduced. An Arrhenius analysis yields a single thermal activation barrier of ${\overline{E}}_{A}=570(6)\phantom{\rule{4pt}{0ex}}\mathrm{K}$ and an attempt frequency ${\overline{\ensuremath{\nu}}}_{0}=309(10)\phantom{\rule{4pt}{0ex}}\mathrm{GHz}$. M\"ossbauer spectroscopy studies with applied transverse magnetic fields up to 5 T reveal a large increase of the fluctuation rate by more than one order of magnitude. In longitudinal magnetic fields, a splitting of the fluctuation rate into two branches is observed consistent with a Zeeman induced modification of the energy levels. The experimental observations are qualitatively reproduced by a single-ion effective spin Hamiltonian analysis assuming a ${\mathrm{Fe}}^{1+}\phantom{\rule{4pt}{0ex}}{d}^{7}$ charge state with the unquenched orbital moment and a $J=7/2$ ground state. It is demonstrated that a weak axial single-ion anisotropy $D$ of the order of a few Kelvin can cause a two orders of magnitude larger energy barrier for longitudinal spin fluctuations.

Coexistence of Spin-Lattice Relaxation and Phonon-Bottleneck Processes in GdIII -Phthlocyaninato Triple-Decker Complexes under Highly Diluted Conditions.

Gd3+ complexes have been shown to undergo unusual slow magnetic relaxation processes similar to those of single-molecule magnets (SMMs), even though Gd3+ does not exhibit strong magnetic anisotropy. To reveal the origin of the slow magnetic relaxation of Gd3+ complexes, we have investigated the magnetic properties and heat capacities of two Gd3+ -phthalocyaninato triple-decker complexes, one of which has intramolecular Gd3+ -Gd3+ interactions and the other does not. It was found that the Gd3+ -Gd3+ interactions accelerate the magnetic relaxation processes. In addition, magnetically diluted samples, prepared by doping a small amount of the Gd3+ complexes into a large amount of diamagnetic Y3+ complexes, underwent dual magnetic relaxation processes. A detailed dynamic magnetic analysis revealed that the coexistence of spin-lattice relaxation and phonon-bottleneck processes is the origin of the dual magnetic relaxation processes.

Controlling Electron Spin Decoherence in Nd-based Complexes via Symmetry Selection.

SummaryLong decoherence time is a key consideration for molecular magnets in the application of the quantum computation. Although previous studies have shown that the local symmetry of spin carriers plays a crucial part in the spin-lattice relaxation process, its role in the spin decoherence is still unclear. Herein, two nine-coordinated capped square antiprism neodymium moieties [Nd(CO3)4H2O]5– with slightly different local symmetries, C1 versus C4 (1 and 2), are reported, which feature in the easy-plane magnetic anisotropy as shown by the high-frequency electron paramagnetic resonance (HF-EPR) studies. Detailed analysis of the relaxation time suggests that the phonon bottleneck effect is essential to the magnetic relaxation in the crystalline samples of 1 and 2. The 240 GHz Pulsed EPR studies show that the higher symmetry results in longer decoherence times, which is supported by the first principle calculations.

Spin-lattice relaxation processes of transition metal ions in a heavily cobalt doped ZnO: Phonon heating effect

Inversion recovery with electron spin-echo detection has been used to study the electron spin-lattice relaxation rates 1/T1 for transition metal impurities in heavily cobalt-doped hydrothermally grown ZnO single crystals. The relaxation dynamics of Co2+ ions dominates the phonon bottleneck effect in the Orbach-Aminov process, which involves the modulation of the zero-field-splitting tensor. The relaxation mechanism may be treated in terms of phonon heating with fast rate of energy pump from Co2+ spins into the lattice phonon modes. The measurements reveal the cross-relaxation process in which the single Co2+ ions cross-relax to exchange-coupled clusters of cobalt ions. The higher temperature relaxation of Co2+ indicates an additional Orbach-Aminov process via a state of ∼226 cm−1 above the ground state Kramers doublet. It is shown that in this system Co2+ ions play a role of the rapidly relaxing centers, strongly mediating the spin-lattice relaxation of the other transition metal impurities, such as Mn2+ and Fe3+.

Solid state proton spin-lattice relaxation in polycrystalline methylphenanthrenes. IV. 1,4-dimethylphenanthrene.

We present and model the NMR frequency (8.50, 22.5, and 53.0 MHz) and temperature (97-300 K) dependence of the solid state 1H spin-lattice relaxation process in polycrystalline 1,4-dimethylphenanthrene. The solid state gives rise to a situation where methyl group rotation is the only motion on the NMR time scale and the relaxation rates due to the rotations of the 1- and 4-methyl groups are conveniently well-separated in temperature. At these low NMR frequencies, both the slow- and fast-motion limits are observed for the rotation of both methyl groups which allows for a more stringent test of the models. The relaxation is nonexponential as expected when it is caused by methyl group rotation in which case the initial relaxation rate is modeled. Parameters characterizing stretched-exponential fits of the relaxation process are also used both to quantify the degree of nonexponential relaxation and indicate that the observed relaxation is indeed due to the rotation of the two methyl groups. The results are compared with several other polycrystalline methylphenanthrenes and dimethylphenanthrenes. These systems allow for an investigation into how intramolecular and intermolecular interactions between methyl groups and neighboring atoms on the same and neighboring molecules determine the barriers to methyl group rotation.

In-depth investigation of large axial magnetic anisotropy in monometallic 3d complexes using frequency domain magnetic resonance and abinitio methods: a study of trigonal bipyramidal Co(ii).

The magnetic properties of 3d monometallic complexes can be tuned through geometric control, owing to their synthetic accessibility and relative structural simplicity. Monodentate ligands offer great potential for fine-tuning the coordination environment to engineer both the axial and rhombic zero-field splitting (ZFS) parameters. In [CoCl3(DABCO)(HDABCO)] (1), the trigonal bipyramidal Co(ii) centre has two bulky axial ligands and three equatorial chloride ligands. An in-depth experimental and theoretical study of 1 reveals a large easy-plane magnetic anisotropy (+ve D) with a negligible rhombic zero-field splitting (E) due to the strict axial symmetry imposed by the C 3 symmetric ligand and trigonal space group. The large easy-plane magnetic anisotropy (D = +44.5 cm-1) is directly deduced using high-field EPR and frequency-domain magnetic resonance (FDMR) studies. Ab initio calculations reveal a large positive contribution to the D term arising from ground state/excited state mixing of the 4E'' states at ∼4085 cm-1 and a minor contribution from the spin-flip transition as well. The nature of the slow relaxation in 1 is elucidated through analysis of the rates of relaxation of magnetisation, taking into account Raman and direct spin-lattice relaxation processes and Quantum Tunnelling of the Magnetisation (QTM). The terms relating to the direct process and QTM were found based on the fit of the field-dependence of τ at 2 K. Subsequently, these were used as fixed parameters in the fit of the temperature-dependence of τ to obtain the Raman terms. This experimental-theoretical investigation provides further insight into the power of FDMR and ab initio methods for the thorough investigation of magnetic anisotropy. Thus, these results contribute to design criteria for high magnetic anisotropy systems.

Site Symmetries of Cerium Ions in BaWO4 Single Crystals Codoped with Sodium Ions

Barium tungstate crystals are an interesting and relatively new medium for stimulated Raman scattering for applications in Raman shifters of laser radiation. Good quality BaWO4 crystals can be grown by Czochralski technique and doped with rare-earth ions. Doping with trivalent ions requires charge compensation which may be provided, for example, by structural defects or proper codoping with alkaline metal ions. Crystals possess scheelite-like structure with the space group I41/a. Results of the electron paramagnetic resonance (EPR) studies of BaWO4:Ce crystals and crystals codoped with Na are presented in this paper. EPR study was performed in the low temperature range 3 K < T < 50 K for all three planes of single crystals. The EPR spectra were attributed to cerium ions with a fictitious spin S = 1/2. The spin Hamilton (SH) parameters were determined. The values of SH parameters indicate the occurrence of paramagnetic centers in axial and low symmetry. The number of observed EPR lines depends on the selected plane. Based on the roadmap, we have found that one center with axial symmetry and at least two centers with low symmetry appear. The linewidth, ∆B, vs temperature dependence revealed increasing exponential tendency with increasing temperature. It shows 1 phonon at the lower temperatures and Raman + Orbach effect at the higher temperatures. Exponential change of the ΔB could be connected with the spin–lattice relaxation processes involving excited states of Ce3+ ions.

Effect of simvastatin in different concentrations on free radicals in A-2058 human melanoma malignum cells-EPR studies.

The influence of concentration of simvastatin (SIM) on free radicals in A-2058 human melanoma malignum cells was studied. The proliferation assay for melanoma A-2058 cells with SIM in concentration range from 0.1 to 20 µM was performed. SIM in the concentrations of 0.1, 0.3, and 1 μM only slightly changed the growth of A-2058 cells, but the growth of the cells considerably decreased for higher concentrations of SIM. Free radicals in the cells were examined by an X-band (9.3 GHz) electron paramagnetic resonance (EPR) spectroscopy. o-Semiquinone free radicals with g-factors in the range of 2.0060 to 2.0065 were found in A-2058 cells. The asymmetric broad EPR spectra with linewidths (ΔBpp ) from 0.87 to 1.25 mT were measured. The fast spin-lattice relaxation processes characterized all the tested cells. The free radical concentrations in the all A-2058 cells cultured with SIM were lower than in the control cells. The quenching of free radicals in A-2058 cells depended on concentration of SIM. This effect was the weakest for concentration of SIM of 3 μM. The strongest decrease of free radical concentration caused SIM in concentration of 1 μM.

Rouse dynamics in PEO-PPO-PEO block-copolymers in aqueous solution as observed through fast field-cycling NMR relaxometry

We present a proton fast field-cycling (FFC) NMR relaxometry study of the molecular dynamics in three different deuterated water-dispersed triblock copolymers of ethylene oxide (EO) and propylene oxide (PO):EO80PO27EO80(F68), EO141PO44EO141 (F108), and EO101PO56EO101(F127). Independently of the phase and molecular arrangement, bi-exponential decays of the magnetization during the spin-lattice relaxation process could be observed for F127, while mono-exponential decays were measured for F68 and F108. This fact has been attributed to the relative ratio of PEO and PPO protons for each case. In F127, each component of the magnetization decay could be associated with a particular block of the co-polymer. A direct consequence of this fact is the independent characterization of the molecular dynamics of each block. It was found that the dominant relaxation mechanism can be attributed to the Rouse model, and it seems to be independent on whether the molecules are incorporated into a micelle, or as individual unimers in the aqueous solution. The experimental results and the provided explanation are consistent with entanglement-free self-assembled structures, and a fast exchange of unimers between the micellar structure and the solvent. This particular feature was also investigated in F68 and F108, although for these cases a mono-exponential decay of the magnetization was observed. NMR relaxometry results are complemented with other relaxation experiments in the rotating frame, NMR spectroscopy and atomic-force microscopy.

EPR Study of Sc2SiO5:Nd143 Isotopically Pure Impurity Crystals

The Sc2SiO5 single crystals doped with 0.001 at.% of the 143Nd3+ ion were studied by continuous-wave and pulse electron paramagnetic resonance methods. The g-tensors and hyperfine structure tensors for two magnetically non-equivalent Nd ions were obtained. The spin–spin and spin–lattice relaxation times were measured at 9.82 GHz in the temperature range from 4 to 10 K. It was established that three relaxation processes contribute to the spin–lattice relaxation processes. There are one-phonon spin–phonon interaction, two-phonon Raman interaction and two-phonon Orbach–Aminov relaxation processes. It was established that spin–spin relaxation time is of the same magnitude for neodymium ion doped in Sc2SiO5 and in Y2SiO5.

Dispersion of Water Proton Spin–Lattice Relaxation Rates in Aqueous Solutions of Multiwall Carbon Nanotubes (MWCNTs) Stabilized via Alkyloxymethylimidazolium Surfactants

Carbon nanotubes and a number of other carbon nanomaterials have a tendency to aggregate, which often resulted in difficulties of dispersion of these nanomaterials in aqueous solutions. The ability of dicationic (gemini) surfactants to disperse multiwall carbon nanotubes in water and the dynamic processes taking place at the water–multiwall carbon nanotubes (MWCTs) interface are studied. Stable dispersions of multiwall carbon nanotubes with selected gemini surfactants (1,1′-(1,6-hexanediyl)bis(3-alkyloxymethylimidazolium) dichlorides) were prepared and characterized by nuclear magnetic relaxation dispersion (NMRD), NMR diffusometry, scanning and transmission electron microscopy, and Fourier transform infrared spectroscopy. The addition of multiwall carbon nanotubes to aqueous solutions of studied gemini surfactants leads to significant paramagnetic enhancement of the spin–lattice relaxation processes, which gets more pronounced with increasing concentration of well-dispersed MWNTs in water. The dominant role of outer sphere (OS) relaxation mechanism in total observed R1, governed by two-dimensional diffusion of water on the carbon nanotube surface in the vicinity of paramagnetic centers incorporated in the MWCNTs’ sidewalls (mainly of iron origin), was assumed to explain NMRD data. The NMR diffusion experiments confirm the existence of restricted water diffusion in the studied supernatants. The NMR diffusion results are consistent with the FTIR and NMR proton spin–lattice relaxation dispersion in which the more effective R1 dispersion noticed for the sample with IMIC6C12 was ascribed to the better accessibility of water molecules to the surface of the MWCNTs.

Comparative EPR studies of free radicals in melanin synthesized by Bacillus weihenstephanensis soil strains

EPR spectroscopy was used to examine the properties of and free radical concentrations in atypical water-soluble melanin-like pigments from Bacillus weihenstephanensis strains. The same EPR spectral shape was observed in bacterial melanins as in eumelanin. The EPR lines were homogeneously broadened. Continuous microwave saturation of the EPR lines indicated slow spin-lattice relaxation processes in the samples. Strong dipolar interactions characterized the tested melanin samples. Higher free radical concentrations were found in bacterial melanin than in synthetic melanin. The free radical concentrations in melanin from B. weihenstephanensis increased in the following order: strain JAS 81/4<JAS 83/3<JAS 86/1<JAS 39/1.

Electron paramagnetic resonance in YbNiAl2 single crystals with strong magnetic anisotropy

Anisotropy in the magnetic properties of YbNiAl2 intermetallide has been studied. Electron paramagnetic resonance (EPR) signals assigned to the localized magnetic moments of trivalent ytterbium have been detected at temperatures below 20 K. Spin–lattice relaxation processes like the Orbach–Aminov process with participation of the first excited Stark sublevel of the Yb3+ ion with an energy of 96 K govern electron–spin dynamics and the disappearance of spectrum lines with a further increase in temperature. Strong magnetic anisotropy effects are discussed as a main reason for the appearance of electron paramagnetic resonance.

Zero-field studies of spin–lattice relaxation processes in non-Kramers doublet of LiF:Ni2+

We use the inversion recovery technique with electron-spin-echo detection in order to study the non-resonant cross-relaxation of Ni2+–VLi with a faster relaxers—the exchange-coupled clusters of Ni2+ ions. An analysis of the results revealed a very high relaxation rate in non-Kramers doublet of LiF:Ni2+. The effect of a magnetic field on the spin–lattice relaxation of Ni2+ has estimated by comparing the results obtained for non-Kramers doublet around zero-magnetic field and for resonance at ~394 mT (X-band microwave frequency).

Solid-State NMR Study of Poly(3-Hydroxybutyrate) and Ecoflex reser Blends

Biodegradable blends of poly(3-hydroxybutyrate) and aromatic-aliphatic co-polyester Ecoflex® were studied by means of basic solid-state NMR techniques. C NMR spectra pointed at existence of individual components in blends, however, existence of regions in which components affect each other was also deduced from changes of shape of some spectral lines. Analysis of proton spin–lattice relaxation process in laboratory frame running in blends with different fractions of components revealed poor miscibility of these polymers. The domain size of components was calculated based on the values of spin–lattice relaxation times in laboratory frame. Spin–lattice relaxation process in the rotating frame of Ecoflex® proton spin system was only slightly influenced by the blending. Incompatibility of these polymers was confirmed by all realized experiments.