Quantum dynamics of Mn2+ in dimethylammonium magnesium formate.

Dimethylammonium magnesium formate, [(CH3)2NH2][Mg(HCOO)3] or DMAMgF, is a model used to study high temperature hybrid perovskite-like dielectrics. This compound displays an order-disorder phase transition at about 260 K. Using multifrequency electron spin resonance in continuous wave and pulsed modes, we herein present the quantum dynamics of the Mn2+ ion probe in DMAMgF. In the high temperature paraelectric phase, we observe a large distribution of the zero field splitting that is attributed to the high local disorder and further supported by density functional theory computations. In the low temperature ferroelastic phase, a single structure phase is detected and shown to contain two magnetic structures. The complex electron paramagnetic resonance signals were identified by means of the Rabi oscillation method combined with the crystal field kernel density estimation.

Hydrogen evolution reaction from bare and surface-functionalized few-layered MoS2 nanosheets in acidic and alkaline electrolytes.

Hydrogen is considered as an ideal and sustainable energy carrier because of its high energy density and carbon-free combustion. Electrochemical water splitting is the only solution for uninterrupted, scalable, and sustainable production of hydrogen without carbon emission. However, a large-scale hydrogen production through electrochemical water splitting depends on the availability of earth-abundant electrocatalysts and a suitable electrolyte medium. In this article, we demonstrate that hydrogen evolution reaction (HER) performance of electrocatalytic materials can be controlled by their surface functionalization and selection of a suitable electrolyte solution. Here, we report syntheses of few-layered MoS2 nanosheets, NiO nanoparticles (NPs), and multiwalled carbon nanotubes (MWCNTs) using scalable production methods from earth-abundant materials. Magnetic measurements of as-produced electrocatalyst materials demonstrate that MoS2 nanoflakes are diamagnetic, whereas surface-functionalized MoS2 and its composite with carbon nanotubes have strong ferromagnetism. The HER performance of the few-layered pristine MoS2 nanoflakes, MoS2/NiO NPs, and MoS2/NiO NPs/MWCNT nanocomposite electrocatalysts are studied in acidic and alkaline media. For bare MoS2, the values of overpotential (η10) in alkaline and acidic media are 0.45 and 0.54 V, respectively. Similarly, the values of current density at 0.5 V overpotential are 27 and 6.2 mA/cm2 in alkaline and acidic media, respectively. The surface functionalization acts adversely in the both alkaline and acidic media. MoS2 nanosheets functionalized with NiO NPs also demonstrated excellent performance for oxygen evolution reaction with anodic current of ~60 mA/cm2 and Tafel slope of 78 mVdec-1 in alkaline medium.

Spin dynamics of the S = 5/2 2D triangular antiferromagnet Ba3NbFe3Si2O14.

We report pulse-field magnetization, ac susceptibility, and 100 GHz electron spin resonance (ESR) measurements on the S = 5/2 two-dimensional triangular compound Ba3NbFe3Si2O14 with the Néel temperature T(N) = 26 K. The magnetization curve shows an almost linear increase up to 60 T with no indication of a one-third magnetization plateau. An unusually large frequency dependence of the ac susceptibility in the temperature range of T = 20-100 K reveals a spin-glass behavior or superparamagnetism, signaling the presence of frustration-related slow magnetic fluctuations. The temperature dependence of the ESR linewidth exhibits two distinct critical regimes; (i) ΔH(pp)(T) is proportional to (T-T(N))(-p) with the exponent p = 0.2(1)-0.2(3) for temperatures above 27 K, and (ii) ΔH(pp)(T) is proportional to (T-T*)(-p) with T* = 12 K and p = 0.8(1)-0.8(4) for temperatures between 12 and 27 K. This is interpreted as indicating a dimensional crossover of magnetic interactions and the persistence of short-range correlations with a helically ordered state.

Coherent manipulation of electron spins in the {Cu3} spin triangle complex impregnated in nanoporous silicon.

We report on coherent manipulation of electron spins in an antiferromagnetically coupled spin triangle {Cu3-X} (X=As, Sb) impregnated in freestanding nanoporous silicon (NS) by using 240 GHz microwave pulses. Rabi oscillations are observed and the spin coherence time is found to be T(2)=1066 ns at 1.5 K. This demonstrates that the {Cu3-X}:NS hybrid material provides a promising scheme for implementing spin-based quantum gates. By measuring the spin relaxation times of samples with different symmetries and environments we give evidence that a spin chirality is the main decoherence source of spin triangle molecules.

Ab initio studies of the para- and antiferroelectric structures and local polarized configurations in NH4H2PO4.

A study of differently polarized structures relevant to the H-bonded antiferroelectric (AFE) compound NH(4)H(2)PO(4) (ADP) is performed by first-principles calculations in the framework of the density functional theory. The calculated structures for the AFE and paraelectric (PE) phases are found in general good agreement with the available experimental data. We study the energetics and relative stability of different polarized clusters embedded in a PE matrix of ADP. We find that local ferroelectric and AFE clusters are stable and may coexist in the PE phase, which explains the coexistence of both type of microregions determined by electron spin probe measurements above the AFE-PE transition temperature. The dependency with the O-H···O bridge length of the energy barrier heights for proton transfer is studied for coordinated proton displacements along the bridges within clusters of different sizes. This dependency may have implications for the geometric isotopic effects on T(c). We analyze Mulliken orbital and bond populations which confirm the existence of a charge flow within the NH(4)(+) ion, an essential fact for the stabilization of the AFE phase over other possible polarized structures. This charge transfer is correlated with the optimization of the N-H···O bridges and with distortions of the NH(4)(+) group.

Review of chromium (VI) apoptosis, cell-cycle-arrest, and carcinogenesis.

Hexavalent chromium combines with glutathione in chloride intracellular channel carrier to form tetravalent and pentavalent chromium in plasma and organelle membranes. It also combines with NADH/NADPH to form pentavalent chromium in mitochondria. Tetravalent- and pentavalent- chromium (directly and indirectly) mediated DNA double strand breaks activate DNA damage signaling sensors: DNA-dependent-protein-kinase signals p53-dependent intrinsic mitochondrial apoptosis, and ataxia-telangiectasia-mutated and ataxia-telangiectasia-Rad3-related signal cell-arrest for DNA repair. Tetravalent chromium may be the most potent species since it causes DNA breaks and somatic recombination, but not apoptosis. Upon further failure of apoptosis and senescence/DNA-repair, damaged cells may become immortal with loss-of-heterozygosity and genetic plasticity.

Multiphoton coherent manipulation in large-spin qubits.

Large-spin Mn2+ ions (S=5/2) diluted in a nonmagnetic MgO matrix of high crystalline symmetry are used to realize a six-level system that can be operated by means of multiphoton coherent Rabi oscillations. This spin system has a very small anisotropy which can be tuned in situ to reversibly transform the system between harmonic and nonharmonic level configurations. Decoherence effects are strongly suppressed as a result of the quasi-isotropic electron interaction with the crystal field and with the 55Mn nuclear spins. These results suggest new ways of manipulating, reading, and resetting spin quantum states which can be applied to encode a qubit across several quantum levels.

Fluctuation-induced heat release from temperature-quenched nuclear spins near a quantum critical point.

At a quantum critical point (QCP)--a zero-temperature singularity in which a line of continuous phase transition terminates--quantum fluctuations diverge in space and time, leading to exotic phenomena that can be observed at nonzero temperatures. Using a quantum antiferromagnet, we present calorimetric evidence that nuclear spins frozen in a high-temperature nonequilibrium state by temperature quenching are annealed by quantum fluctuations near the QCP. This phenomenon, with readily detectable heat release from the nuclear spins as they are annealed, serves as an excellent marker of a quantum critical region around the QCP and provides a probe of the dynamics of the divergent quantum fluctuations.

Coherent manipulation of electron spins up to ambient temperatures in Cr5+ (S = 1/2) doped K3NbO8.

We report coherent spin manipulation on Cr(5+) (S = 1/2, I = 0) doped K(3)NbO(8), which constitutes a dilute two-level model relevant for use as a spin qubit. Rabi oscillations are observed for the first time in a spin system based on transition metal oxides up to room temperature. At liquid helium temperature the phase coherence relaxation time T2 reaches approximately 10 micros and, with a Rabi frequency of 20 MHz, yields a single-qubit figure of merit Q(M) of about 500. This shows that a diluted ensemble of Cr(5+) (S = 1/2) doped K(3)NbO(8) is a potential candidate for solid-state quantum information processing.

Origin of antiferroelectricity in NH4H2PO4 from first principles.

The low-temperature antiferroelectric (AFE) phase of NH4H2PO4 corresponds to H ordering in O-H-O bridges leading to H2PO4 group polarizations perpendicular to the tetragonal c axis and alternating in chains. We determine the microscopic origin of such order by means of first-principles calculations in the framework of the density functional theory. The formation of N-Hcdots, three dots, centeredO bridges with correlated charge transfers and NH4+ group distortions turn out to be essential in stabilizing the AFE configuration against a c-polarized ferroelectric (FE) phase, as well as other FE states polarized perpendicular to the c axis. These FE states lie only a few meV above the AFE phase, which explains the observation of FE-AFE phase coexistence near the AFE transition.

High resolution 15N NMR of the 225 K phase transition of ammonia borane (NH3BH3): mixed order-disorder and displacive behavior.

We report high resolution 15N NMR probing of the solid-solid phase transition of 15N-labeled ammonia borane (NH3BH3) at 225 K. Both the 15N isotropic chemical shift (delta iso) and the spin-lattice relaxation rate (T1-1) exhibited strong anomalies around 225 K. The analysis of T1-1 using the Bloembergen, Purcell, and Pound model showed that the motional correlation time, tau, increased from about 1 to 100 ps and the corresponding Arrhenius activation energy increased from 6 to 14.5 kJ/mol on going through the transition toward lower temperatures. The temperature dependence of delta iso was interpreted by an extension of the Bayer model. The time scale of the underlying motion was found to be in a reasonable agreement with the T1-1 data. These results imply that the NH3 rotor motion plays a pivotal role in the transition mechanism and that the transition is of both order-disorder and displacive type.

The properties of the [Mn12O12(O2CR)16(H2O)4] single-molecule magnets in truly axial symmetry: [Mn12O12(O2CCH2Br)16(H2O)4].4CH2Cl2.

Detailed studies are reported of a Mn(12) single-molecule magnet (SMM) in truly axial (tetragonal) symmetry. The complex is [Mn(12)O(12)(O(2)CCH(2)Br)(16)(H(2)O)(4)].4CH(2)Cl(2) (2.4CH(2)Cl(2) or Mn(12)-BrAc), obtained by the standard carboxylate substitution method. The complex has an S = 10 ground state, typical of the Mn(12) family, and displays frequency-dependent out-of-phase AC susceptibility signals and hysteresis in single-crystal magnetization vs applied DC field sweeps. Single-crystal high-frequency EPR spectra in frequencies up to 360 GHz exhibit narrow signals that are not overlapping multiplets, in contrast to [Mn(12)O(12)(O(2)CMe)(16)(H(2)O)(4)].2MeCO(2)H.4H(2)O (1 or Mn(12)-Ac), which also crystallizes in an axial (tetragonal) space group but which now is recognized to consist of a mixture of six hydrogen-bonded isomers in the crystal and thus gives multiple, inhomogeneously broadened EPR signals. Similarly, single-crystal (55)Mn NMR spectra on Mn(12)-BrAc display much sharper signals than a single crystal of Mn(12)-Ac, and this allows one Mn(III) signal to show an almost baseline-resolved quintet from quadrupolar splitting ((55)Mn, I = 5/2, 100%), allowing quadrupole coupling parameters (e(2)qQ) to be determined. In addition, it was found that crushing crystals of Mn(12)-BrAc into a microcrystalline powder causes severe broadening and shifts of the NMR resonances, emphasizing the superiority of single-crystal studies. The combined results establish that Mn(12)-BrAc is far superior to Mn(12)-Ac for the study of the intrinsic properties of the Mn(12) family of SMMs in axial symmetry, and for the search for new phenomena such as quantum interference effects caused by higher-order (>2nd-order) transverse terms in the spin Hamiltonian.

Heat capacity and electron spin echo evidence for low frequency vibrational modes and lattice disorder in L-alanine at cryogenic temperatures.

With the view of understanding the low frequency (40-50 cm(-1)) motional processes in L-alanine around 4 K, we have carried out heat capacity (CP) and electron spin echo (ESE) measurements on L-alanine and L-alanine-d7. The obtained CP data show the so-called boson peak (seen as a maximum in CP/T3 versus T plots) in the low temperature region (1.8-20 K). The phase memory time, T(M), and spin lattice relaxation time, T1, of the spin probe, the so-called first stable alanine radical (SAR1), *CHCH3COOH, have been measured between 4 and 105 K. The obtained relaxation rate 1/T1 shows an anomalous increase which coincides with the emergence of a boson peak in the low temperature region (4-20 K). Together, the ESE and the CP data confirm the existence of a thermally activated dynamic orientational disorder in the lattices of both compounds below 20 K. The results help explain the discrepancy between the CP data from powders and single crystals of alanine, as well as the proanomalous relaxation mechanisms for SAR1 in these lattices, and they also provide a mechanism for the spin-lattice relaxation process for SAR1 at cryogenic temperatures.

An EPR method for probing surface magnetic fields, dipolar distances, and magnetization fluctuations in single molecule magnets.

We outline a spectroscopic method for probing the effective magnetic field B on the surface of crystals of the single molecule magnet (SMM) [(C6H15N3)6Fe8(mu3-O)2(mu2-OH)12]Br7(H2O)Br.H2O, (Fe8Br8). This technique utilizes the line shape changes in the EPR spectra of the organic radical 2,2-diphenyl-1-picrylhydrazyl (DPPH) (g = 2.0036, single peak) adsorbed onto the sample. The temperature dependence of the EPR line shifts scale with the sample's magnetization as measured by a SQUID magnetometer. Analysis of the line shape in terms of dipolar coupling between the DPPH and the SMM molecules on the surface, yields their average dipolar distance. The method's potential for measuring the magnetization fluctuation dynamics is briefly pointed out using the SMM [Mn12O12(CH3COO)16(H2O)4].2CH3COOH.4H2O (Mn12-acetate).

Probing magnetic fields on crystals of the nanomagnet Mn12-acetate by electron paramagnetic resonance.

We report on electron paramagnetic resonance (EPR) probing of magnetic fields and magnetic field gradients near the surface of a single crystal of the nanomagnet [Mn12O12(CH3COO)16(H2O)4].2CH3COOH.4H2O (Mn12-Ac). As the EPR probe, we utilized a 0.7 mm x 30 microm x 30 microm fibrous needle of the organic conductor N-methylphenazinium-tetracyanoquinodimethane (NMP-TCNQ), which yields an exceptionally sharp peak, with a 0.2 G (approximately 20 microT) width. In the presence of Mn12-Ac, the probe's peak exhibits splitting on temperature lowering, which depends on the orientation of the Zeeman field relative to the axis of easy magnetization of the employed Mn12-Ac crystal. The shifted peaks yield the magnitude of the magnetic field from Mn12-Ac crystal to which the various fibers of the probe are subjected. In conjunction with electron microscopy, the shifts yield the field gradient at the crystal surface and its change with temperature. For Mn12-Ac at 10 K, the surface magnetic field was measured to be in the mT range and its gradient on the order of 50 T/m.

Definitive spectroscopic determination of the transverse interactions responsible for the magnetic quantum tunneling in Mn(12)-acetate.

We present detailed angle-dependent single crystal electron paramagnetic resonance (EPR) data for field rotations in the hard plane of the S=10 single molecule magnet Mn(12)-acetate. A clear fourfold variation in the resonance positions may be attributed to an intrinsic fourth-order transverse anisotropy (O(4)/(4)). Meanwhile, a fourfold variation of the EPR line shapes confirms a recently proposed model wherein disorder associated with the acetic acid of crystallization induces a locally varying quadratic (rhombic) transverse anisotropy [O (2)/(2) identical with E(S (2)/(x)-S(2)/(y))]. These findings explain most aspects of the magnetic quantum tunneling observed in Mn(12)-acetate.

1-370 GHz EPR linewidths for K3CrO8: a comprehensive test for the Anderson-Weiss model.

Electron paramagnetic resonance (EPR) measurements have been carried out over the frequency range of 1-370 GHz on single crystals of potassium peroxychromate (K3CrO8) with the view of examining the current models of exchange narrowing of EPR signals in solids. K3CrO8 has a simple (tetragonal) lattice structure, can be grown as single crystals pure or diluted with an isostructural diamagnetic host K3NbO8, and its paramagnetism can be described by a very simple (S = 12, I = 0) spin Hamiltonian. The measurements were made at various orientations of single crystals in the Zeeman field, with emphasis on the principal directions of the g-tensor. For essentially all orientations, the linewidth decreases monotonically for measurements at resonance frequencies, omega0, from 1 to about 100 GHz, and then starts to increase at higher omega0. In order to delineate the spin exchange effects from other sources of line broadening, the measurements were repeated with a diluted spin system, K3NbO8 containing approximately/= 0.5 mole % of K3CrO8, representing the broadening effect of all the magnetic field dependent terms, such as the broadening due to the g-strain and sample holder/waveguide magnetization at the high field utilized, up to 14 T. Using these data, the K3CrO8 linewidths were analyzed in terms of the current models of spin exchange narrowing in three-dimensional systems. A reasonably good agreement was found with the Anderson-Weiss model, when modified for various line broadening effects. The accuracy of the analysis procedure was confirmed by the comparison of the presently determined values of the exchange constant, J, and the dipolar field, Hp, with their values obtained by dc magnetic susceptibility measurements and theoretical analysis, respectively; the agreement was within 5% for J (=1.35 K) and about 25% for Hp (160 G). However, some deviations and unusual splittings were noted in measurements at 370 GHz, whose origin remains unclear.

Augmentation of pulmonary reactions to quartz inhalation by trace amounts of iron-containing particles.

Fracturing quartz produces silica-based radicals on the fracture planes and generates hydroxyl radicals (.OH) in aqueous media. .OH production has been shown to be directly associated with quartz-induced cell damage and phagocyte activation in vitro. This .OH production in vitro is inhibited by desferrioxamine mesylate, an Fe chelator, indicating involvement of a Fenton-like reaction. Our objective was to determine if Fe contamination increased the ability of inhaled quartz to cause inflammation and lung injury. Male Fischer 344 rats were exposed 5 hr/day for 10 days to filtered air, 20 mg/m3 freshly milled quartz (57 ppm Fe), or 20 mg/m3 freshly milled quartz contaminated with Fe (430 ppm Fe). High Fe contamination of quartz produced approximately 57% more reactive species in water than quartz with low Fe contamination. Compared to inhalation of quartz with low Fe contamination, high Fe contamination of quartz resulted in increases in the following responses: leukocyte recruitment (537%), lavageable red blood cells (157%), macrophage production of oxygen radicals measured by electron spin resonance or chemiluminescence (32 or 90%, respectively), nitric oxide production by macrophages (71%), and lipid peroxidation of lung tissue (38%). These results suggest that inhalation of freshly fractured quartz contaminated with trace levels of Fe may be more pathogenic than inhalation of quartz alone.

Synthesis of Cr(IV)-GSH, its identification and its free hydroxyl radical generation: a model compound for Cr(VI) carcinogenicity.

Current models of Cr(VI) carcinogenesis suggest an important role for Cr(IV) as an intermediate, toxic, carcinogenic species, but direct chemical evidence has been lacking. This is because Cr(IV) is a highly reactive oxidation state of Cr and few Cr(IV)-based compounds are known that can be used as a model compound containing a biological ligand. This study reports the isolation of such a stable Cr(IV) complex. The Cr(IV)-GSH complex has been synthesized through the reaction of Cr(VI) with GSH. Its electron paramagnetic resonance (EPR) spectrum exhibits g = 1.9629 and a peak-to-peak line width of 480 G in aqueous medium as well as in the powder form. Magnetic susceptibility measurements showed that the compound has a magnetic moment of 2.53 Bohr magneton per Cr, establishing that the Cr ion has two unpaired electrons, hence its identity as Cr(IV). The Cr(IV)-GSH complex is able to generate hydroxyl (.OH) radical in the presence of molecular oxygen in aqueous medium. Catalase inhibited the .OH radical generation while H2O2 enhanced it, indicating that the .OH radical was generated via a Fenton-like reaction, H2O2 being generated as an intermediate in the reduction of molecular oxygen. Metal ion chelators, deferoxamine and 1,10-phenanthroline, attenuated the generation of Cr(IV)-mediated .OH radical. In the case of deferoxamine, a deferoxamine-derived free radical was generated as shown by EPR measurements. The results imply that Cr(IV) may play an important role in the mechanism of Cr(VI)-induced carcinogenesis and Cr(IV)-GSH can be used as a model compound to study the role of Cr(IV) in this mechanism.

Squaric acid as an internal standard for temperature measurements in 13C MAS NMR.

Squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) is suggested as an internal standard for temperature measurements in 13C MAS NMR studies in the temperature range from 373 K to 520 K. Compared to previously utilized standards, squaric acid has several important advantages, such as fast kinetics of the phase transition, higher temperature range for 13C studies, and an almost constant sample volume through the transition temperature range. Thus, we found squaric acid to be suitable for the probe calibration with the reference temperature at 373.2 K. Moreover, upon partial deuteration the reference temperature can be gradually increased to 520 K. Additionally, the described procedure makes it possible to quantitatively estimate the temperature gradient across the sample. We also discuss the effect of spinning related stress on the temperature measurement technique and how this effect could be minimized.