Averaged Coupling Constants Research Articles

Near-zero-field magnetoresistance measurements: A simple method to track atomic-scale defects involved in metal-oxide-semiconductor device reliability.

We demonstrate the ability of a relatively new analytical technique, near-zero-field magnetoresistance (NZFMR), to track atomic-scale phenomena involved in the high-field stressing damage of fully processed Si metal-oxide-semiconductor field-effect transistors. We show that the technique is sensitive to both the Pb0 and Pb1 dangling bond centers and that the presence of both centers can be inferred through NZFMR via hyperfine interactions with the central 29Si atoms of the dangling bonds. The NZFMR results also provide evidence for the redistribution of mobile hydrogen atoms at the Si/SiO2 interface and also a potential change in the average dipolar coupling constant between electrons in neighboring defects. This work shows that NZFMR offers significant analytical power for studying technologically relevant semiconductor device reliability problems and has advantages in experimental simplicity over comparable techniques.

Analysis and information content of quadrupolar NMR in glasses: 25Mg NMR in vitreous MgSiO3 and CaMgSi2O6

The static wideline and high-resolution magic angle spinning (MAS) 25Mg NMR lineshapes measured for isotopically enriched enstatite and diopside glasses indicate a wide distribution of the electric-field gradient (EFG) components at the 25Mg position caused by disorder. The correct characterization of this distribution requires simulations with special attention paid to the experimental parameters. Here, both the static spectra obtained by wideband excitation and the MAS-NMR spectra obtained via rotor-synchronized Hahn spin echo acquisition were successfully simulated with the Czjzek distribution model, using one consistent set of parameters. Average nuclear electric quadrupole coupling constants near 8 MHz and a distribution width around 4 MHz were obtained for both materials, which suggests that earlier results on these glasses need to be re-examined. The results of this study outline a general strategy for characterizing the local environments of strongly coupled quadrupolar nuclei in amorphous and glassy materials. Despite the discrepancies between the interaction parameters extracted from our data and those published in earlier NMR work, the best fit to the data indicate an average isotropic chemical shift near 13 ppm (vs. aqueous MgCl2 solution) for both the enstatite and diopside glasses. Assuming the applicability of the current database relating the 25Mg chemical shifts with coordination numbers in crystalline compounds, this value suggests that the Mg2+ ions are six-coordinated. This conclusion, however, is based on the simplifying assumption that the 25Mg spectrum comprises a Czjzek distribution centered at a single isotropic chemical shift value and stands in contrast to the results of recent isotope-selective neutron diffraction studies which give an average Mg-O coordination number of 4.4–4.5 for both glasses. However, reasonable fits to the MAS-NMR spectra can also be obtained when constraining the average isotropic chemical shift to 50 ppm, a value typical of four-coordinated Mg. We conclude that multiple Mg sites with different coordination numbers may well be present and that, in the present glasses, 25Mg NMR at typically used spinning rates and magnetic field strengths (20 kHz, 14.1 T) is not capable of resolving them due to excessive broadening by quadrupolar interactions.

Quantum Squeezing of the Field of a Single-Atom Laser under Conditions of a Variable Coupling Constant

A nonstationary regime of squeezed-light generation by a single-atom laser is investigated. Dependences of the quantum-squeezing parameter and radiation intensity on modulation frequency of the atom–field coupling constant are obtained. It is demonstrated that a resonance appears at the modulation frequency equal to twice the average coupling constant, which leads to a more efficient quantum squeezing in a nonstationary harmonic regime than in the case of a stationary regime for the same values of the relaxation and pump parameters.

Superconductivity in YIn3 under positive pressure

Positive hydrostatic pressure was applied on YIn3 and variation in superconducting transition temperature (Tc) and average coupling constant (λep) was observed. The variation in phonon dispersion relation, Eliashberg spectral function, phonon DOS and average logarithmic phonon frequency was studied with an increase in positive hydrostatic pressure. The dispersion relation for YIn3 under ambient and all applied positive pressure shows positive frequency for all modes of vibrations signifying the structural stability of YIn3 under all applied pressures.

Variation of Superconducting Transition Temperature of YSn3 Under Negative Pressure

First-principle calculations of YSn3 were performed under both ambient pressure and applied negative hydrostatic pressure. The phonon dispersion relation under all applied pressures was found to have a positive frequency. The superconducting transition temperature (Tc) and average electron-phonon coupling constant (λep) was found to increase with increase in applied negative hydrostatic pressure. The Eliashberg spectral function was also calculated under various applied negative hydrostatic pressures.

SCoT: Swept coherence transfer for quantitative heteronuclear 2D NMR

Nuclear magnetic resonance (NMR) spectroscopy is frequently applied in quantitative chemical analysis (qNMR). It is easy to measure one-dimensional (1D) NMR spectra in a quantitative regime (with appropriately long relaxation delays and acquisition times); however, their applicability is limited in the case of complex samples with severe peak overlap. Two-dimensional (2D) NMR solves the overlap problem, but at the cost of biasing peak intensities and hence quantitativeness. This is partly due to the uneven coherence transfer between excited/detected 1H nuclei and the heteronuclei coupled to them (typically 13C). In the traditional approach, the transfer occurs via the evolution of a spin system state under the J-coupling Hamiltonian during a delay of a fixed length. The delay length is set on the basis of the predicted average coupling constant in the sample. This leads to disturbances for pairs of nuclei with coupling constants deviating from this average. Here, we present a novel approach based on non-standard processing of the data acquired in experiments, where the coherence transfer delay is co-incremented with non-uniformly sampled evolution time. This method allows us to obtain the optimal transfer for all resonances, which improves quantitativeness. We demonstrate the concept for the coherence transfer and multiplicity-edit delays in a heteronuclear single-quantum correlation experiment (HSQC).

Filling the Missing Links of M3n Prototype 3d-4f and 4f Cyclic Coordination Cages: Syntheses, Structures, and Magnetic Properties of the Ni10Ln5 and the Er3n Wheels

In this paper, we proposed a number rule for 3d-4f and 4f cyclic coordination cages (CCCs); that is, CCCs consisting of vertex-sharing M4(μ3-OH)4 (M = 3d transition metal or 4f lanthanide ions) units should have 3 × n metal centers (abbreviated M3n), where n represents the number of the M4(μ3-OH)4 subunits. Under this number rule we reasoned that some species of CCCs, for example, the pentadecanuclear 3d-4f wheel and the pure 4f wheels with 9 or 18 centers, should practically have existed. However, there are no such complexes reported in the literature. To realize such CCCs we employed a mixed-ligand approach, that is, to simultaneously use the primary and the ancillary ligands for syntheses. This approach successfully leads to the isolation of two families of CCCs, namely, the Ni10Ln5 (Ln = Gd and Y) mixed-metal wheels and the Er3n (n = 4, 5, and 6) pure 4f metal wheels. These two families of CCCs unambiguously fill the missing links of the M3n prototype CCCs. Moreover, dominated ferromagnetic interaction indicates high ground-spin state for the Gd5Ni10 wheel. The ferromagnetic interactions between the nickel centers are verified using the diamagnetic Y(III) analogue, which reveals an averaged coupling constant (J = 2.7 cm-1), while accompanied by a large negative zero-field splitting parameter (D = -6.1 cm-1) for single Ni(II) ions. Interestingly, the Y(III)-diluted Er12 wheel shows slow magnetic relaxation behavior, presumably indicating the magnetically anisotropic nature of the erbium(III) ions.

Dynamic structure of organic compounds in solution according to NMR data and quantum chemical calculations: II. Styrene

Dynamic structure of Soman diastereoisomers has been studied with the goal of obtaining accurate information to simulate molecular mechanisms of its action on living systems. The potential energy surface for internal rotation about the single P–O and O–C bonds has been constructed in terms of the Moller–Plesset second-order perturbation theory using 6-311G(d,p) basis set. The relative contributions of different conformers have been estimated by solving the vibrational problem according to the large-amplitude vibration model. The conformational dependences of the 4 J CF and 3 J CP coupling constants for the S,S and S,R diastereoisomers of Soman have been calculated at the FPT DFT B3LYP/6-311++G(2df,2p) level of theory. The calculated vibrationally averaged coupling constants have been compared with the available experimental data to determine the structure of the most toxic Soman stereoisomer.

Synthesis of Molecular Seesaw Balances and the Evaluation of Pyridinium-π Interactions.

A series of molecular seesaw balances 1-5 have been developed to measure the relative strength of pyridinium-π (cation-π) interactions. The cycloaddition of 1-azaanthracene and o-quinodimethane under microwave irradiation afforded the efficient synthesis of 1 and 5. Introduction of substituents to the pyridine ring of balance 1 was achieved to produce 2-4 in good yields. Anion exchange of 1·MeI afforded 1·MeX with a variety of counteranions (X = Cl, Br, I, BF4, PF6, OAc). These balances adopt two distinct conformers, A and B, which are stabilized by a cation-π interaction and a π-π interaction, respectively. The conformer ratio was determined on the basis of the observed averaged 3J coupling constants for H1-C-C-H2 by comparison with the boundary JA and JB values, which were estimated by applying the Carplus-Altona equation to the dihedral angles of the optimized conformers A and B. The effects of the solvent, substituent and counteranion on the ΔG values were elucidated using these molecular balances. Thermodynamic parameters obtained from a van't Hoff plot as well as the electrostatic potential maps for both conformers A and B of the molecular balances helped us to better understand the obtained results.

Defect luminescence and lattice strain in Mn2+ doped ZnGa2O4

Undoped and Mn2+ doped ZnGa2O4 phosphors were prepared by solution combustion method and characterized by XRD, SEM, luminescence and electron paramagnetic resonance (EPR) techniques. Based on XRD results, it is inferred that, strain in ZnGa2O4 host lattice increases with incorporation of Mn2+ ions in the lattice. Mn2+ doping at concentration levels investigated, lead to significant reduction in the defect emission and this has been attributed to the formation of higher oxidation states of Mn ions in the lattice. Electron Paramagnetic Resonance studies confirmed that majority of Mn ions exist as Mn2+ species and they occupy tetrahedral Zn2+ site in ZnGa2O4 lattice with an average hyperfine coupling constant, Aiso∼82G.

Fe(CN)5(isoniazid)]3 −: An iron isoniazid complex with redox behavior implicated in tuberculosis therapy

Tuberculosis has re-emerged as a worldwide threat, which has motivated the development of new drugs. The antituberculosis complex Na3[Fe(CN)5(isoniazid)] (IQG607) in particular is of interest on account of its ability to overcome resistance. IQG607 has the potential for redox-mediated-activation, in which an acylpyridine (isonicotinoyl) radical could be generated without assistance from the mycobacterial KatG enzyme. Here, we have investigated the reactivity of IQG607 toward hydrogen peroxide and superoxide, well-known intracellular oxidizing agents that could play a key role in the redox-mediated-activation of this compound. HPLC, NMR and electronic spectroscopy studies showed a very fast oxidation rate for bound isoniazid, over 460-fold faster than free isoniazid oxidation. A series of EPR spin traps were used for detection of isonicotinoyl and derived radicals bound to iron. This is the first report for an isonicotinoyl radical bound to a metal complex, supported by 14N and 1H hyperfine splittings for the POBN and PBN trapped radicals. POBN and PBN exhibited average hyperfine coupling constants of aN=15.6, aH=2.8 and aN=15.4, aH=4.7, respectively, which are in close agreement to the isonicotinoyl radical. Radical generation is thought to play a major role in the mechanism of action of isoniazid and this work provides strong evidence for its production within IQG607, which, along with biological and chemical oxidation data, support a redox-mediated activation mechanism. More generally the concept of redox activation of metallo prodrugs could be applied more widely for the design of therapeutic agents with novel mechanisms of action.

Investigating vibrational anharmonic couplings in cyanide-bridged transition metal mixed valence complexes using two-dimensional infrared spectroscopy

Using polarization-selective two-dimensional infrared (2D IR) spectroscopy, we measure anharmonic couplings and angles between the transition dipole moments of the four cyanide stretching (νCN) vibrations found in [(NH3)5Ru(III)NCFe(II)(CN)5](-) (FeRu) dissolved in D2O and formamide and [(NC)5Fe(II)CNPt(IV)(NH3)4NCFe(II)(CN)5](4-) (FePtFe) dissolved in D2O. These cyanide-bridged transition metal complexes serve as model systems for studying the role of high frequency vibrational modes in ultrafast photoinduced charge transfer reactions. Here, we focus on the spectroscopy of the νCN modes in the electronic ground state. The FTIR spectra of the νCN modes of the bimetallic and trimetallic systems are strikingly different in terms of frequencies, amplitudes, and lineshapes. The experimental 2D IR spectra of FeRu and FePtFe and their fits reveal a set of weakly coupled anharmonic νCN modes. The vibrational mode anharmonicities of the individual νCN modes range from 14 to 28 cm(-1). The mixed-mode anharmonicities range from 2 to 14 cm(-1). In general, the bridging νCN mode is most weakly coupled to the radial νCN mode, which involves the terminal CN ligands. Measurement of the relative transition dipole moments of the four νCN modes reveal that the FeRu molecule is almost linear in solution when dissolved in formamide, but it assumes a bent geometry when dissolved in D2O. The νCN modes are modelled as bilinearly coupled anharmonic oscillators with an average coupling constant of 6 cm(-1). This study elucidates the role of the solvent in modulating the molecular geometry and the anharmonic vibrational couplings between the νCN modes in cyanide-bridged transition metal mixed valence complexes.

Comparative study of electronic structure of cubic and hexagonal phases of Re3W as non-centrosymmetric and centrosymmetric low-TC superconductors

The comparative study of structural properties, stability and electronic structure of cubic and hexagonal phases of the intermetallic Re3W, which have attracted recently interest as non-centrosymmetric and centrosymmetric low-TC superconductors, was performed by means of the first-principles calculations. The optimized lattice constants, cell volumes, theoretical density, formation energies and cohesive energies, as well as electronic densities of states are obtained and analyzed. We have found that the lowering of TC (as going from h-Re3W with TC ∼ 9.4 K to c-Re3W with TC ∼ 7.8 K) correlates with lowering of the near-Fermi density of states (of the mixed W 5d + Re 5d type with admixtures of (Re,W) 6s, 6p states) owing to lowering of contributions of W 5d and Re 6p states. Our estimations of average electron-phonon coupling constants λ show that these phases are near to the weak coupling limit, with some growth of constant λ for h-Re3W (λ ∼ 0.60) as compared with c-Re3W (λ ∼ 0.42).

The 16 CB11(CH3)n(CD3)12–n• Radicals with 5-Fold Substitution Symmetry: Spin Density Distribution in CB11Me12•

The syntheses of all 16 CB(11)(CH(3))(n)(CD(3))(12-n)(•) radicals with 5-fold substitution symmetry are described. The variation in the width of their broad and featureless electron paramagnetic resonance signals as a function of the deuteriation pattern is used to deduce the relative values of the average hyperfine coupling constants a(H) of the hydrogen atoms in the ipso (1), ortho (2-6), meta (7-11), and para (12) methyl groups, a(H)(i):a(H)(o):a(H)(m):a(H)(p) = (0.18 ± 0.09):(0.71 ± 0.02):(1.00 ± 0.03):(0.52 ± 0.05), and these can be compared with ratios expected from a B3LYP/EPRII calculation, 0.04:0.55:1:0.51.

Disorder-induced transition betweens±ands++states in two-band superconductors

We have reexamined the problem of disorder in two-band superconductors, and shown within the framework of the T-matrix approximation, that the suppression of T_c can be described by a single parameter depending on the intraband and interband impurity scattering rates. T_c is shown to be more robust against nonmagnetic impurities than would be predicted in the trivial extension of Abrikosov-Gor'kov theory. We find a disorder-induced transition from the s_{\pm} state to a gapless and then to a fully gapped s_{++} state, controlled by a single parameter -- the sign of the average coupling constant <\lambda> . We argue that this transition has strong implications for experiments.

Solid-State NMR Studies of the Local Structure of NaAlH4/C Nanocomposites at Different Stages of Hydrogen Desorption and Rehydrogenation

Structural properties of NaAlH4/C nanocomposites were studied using 23Na and 27Al solid-state NMR. The samples were synthesized by melt infiltration of a highly porous carbon support, with typical pore sizes of 2−3 nm. Physical mixtures of high surface carbon with alanates in different stages of hydrogen desorption show somewhat broadened resonances and a small negative chemical shift compared to pure alanates. This is most likely caused by a susceptibility effect of the carbon support material, which shields and distorts the applied magnetic field. After melt infiltration, 23Na and 27Al spectra are broadened with a small downfield average shift, which is mainly caused by a chemical shift distribution and is explained by a larger disorder in the nanoconfined materials and a possible charge transfer to the carbon. Our measurements show that the local structure of the nanoconfined alanate is the similar to bulk alanate because a comparable chemical shift and average quadrupolar coupling constant is found. In contrast to bulk alanates, in partly desorbed nanocomposite samples no Na3AlH6 is detected. Together with a single release peak observed by dehydrogenation experiments, this points toward a desorption in one single step. 23Na spectra of completely desorbed NaAlH4/C and NaH/C nanocomposites confirm the formation of metallic sodium at lower temperatures than those observed for bulk alanates. The structural properties observed with solid-state NMR of the nanoconfined alanate are restored after a rehydrogenation cycle. This demonstrates that the dehydrogenation of the NaAlH4/C nanocomposite is reversible, even without a Ti-based catalyst.

The NMR line shape of a gas of hydrogen molecules in nanopores

We consider a closed nanopore filled with hydrogen gas in an external magnetic field. Only hydrogen molecules with spin I = 1 contribute to nuclear magnetic resonance (NMR) spin dynamics. Rapid molecular diffusion leads to partial averaging of dipole-dipole interactions (DDI) of spins I = 1 of different molecules. A method for the calculation of the NMR line shape of a hydrogen gas in nanopores is developed. Significant technical difficulties in calculations of the NMR line shape of the system of spins I = 1 coupled by DDI can be overcome with the introduction of a self-interaction with an averaged DDI coupling constant. The accuracy of this procedure is proportional to \( 1/\sqrt N \), where N is the number of hydrogen molecules in the nanocavity. In this approximation the NMR line is Gaussian. The second and fourth moments of the NMR line shape are calculated both from the known line shape and with the Van Vleck theory. They coincide up to the terms of the order of 1/N. The obtained results are in good agreement with experimental data for thin films with ellipsoidal nanopores. The developed theory allows one to extract information about sizes, shapes and orientations of nanopores in solids.

Optical Transition Linewidths due to Piezoelectric Phonon Scattering in Two-Dimensional Electron Systems

Utilizing the optical transition formula derived by a projection method on the linear response scheme, we obtain the optical transition linewidths for the electron system in square well due to piezoelectric phonon scattering in CdS and ZnS. We find that the widths increase with the temperature, but decrease as the well width increases for both materials. We also find that the widths decrease as the electron density increases, and the widths in CdS are larger than those in ZnS since the average electromechanical coupling constant is larger.

Prediction of nitroxide hyperfine coupling constants in solution from combined nanosecond scale simulations and quantum computations

We present a combined theoretical approach based on analyzing molecular dynamics trajectories (at the nanosecond scale) generated by use of classical polarizable force fields and on quantum calculations to compute averaged hyperfine coupling constants. That method is used to estimate the constant of a prototypical nitroxide: the dimethylnitroxide. The molecule is embedded during the simulations in a cubic box containing about 500 water molecules and the molecular dynamics is generated using periodic conditions. Once the trajectories are achieved, the nitroxide and its first hydration shell molecules are extracted, and the coupling constants are computed by considering the latter aggregates by means of quantum computations. However, all the water molecules of the bulk are also accounted for during those computations by means of the electrostatic potential fitted method. Our results exhibit that in order to predict accurate and reliable coupling constants, one needs to describe carefully the out-of-plane motion of the nitroxide nitrogen and to sample trajectories with a time interval of 400 fs at least to generate an uncorrelated large set of nitroxide structures. Compared to Car-Parrinello molecular dynamics techniques, our approach can be used readily to compute hyperfine coupling constants of large systems, such as nitroxides of great size interacting with macromolecules such as proteins or polymers.

Variation of Average g Values and Effective Exchange Coupling Constants among [2Fe−2S] Clusters: A Density Functional Theory Study of the Impact of Localization (Trapping Forces) versus Delocalization (Double-Exchange) as Competing Factors

A phenomenological model aimed at rationalizing variations in both average g-tensor values (gav identical with 1/3Sigmaigi ) and effective exchange coupling constants Jeff (defined as two-thirds of the energy difference between the S = 3/2 and S = 1/2 spin states) has been derived in order to describe the great variety of magnetic properties exhibited by reduced [2Fe-2S] clusters in proteins. The key quantity in the present analysis is the ratio Delta E/B computed from two competing terms. Delta Ecomprises various effects that result in trapping-site asymmetries: vibronic coupling and the chemical nature (S/N/O) and conformations of the ligands on the one hand and solvation terms, the hydrogen bonding network, etc., on the other. All of these additive terms (in a "bottom-up" approach) favor valence localization of the reducing electron onto one of the two iron sites. In contrast, the B term is the double-exchange term, which favors electronic delocalization. Both gav and Jeff can be expressed as functions of Delta E/ B. We have also shown that electronic localization generally favors small gav and large Jeff values (while the opposite is true for electronic delocalization) in a comparative study of the spectroscopic features of plant-type ferredoxins (Fd's) and Rieske centers (and related mutants). Two other types of problems were particularly challenging. The first of these involved deprotonated Rieske centers and the xanthine oxidase clusters II, which are characterized by very small Jeff values (40-45 cm (-1) with a J S A. S B model) correlated with unusually large gav values (in the range 1.97-2.01) as a result of an antisymmetric exchange coupling mechanism. The second concerned the analogous Fd's from Clostridium pasteurianum (Cp) and Aquifex aeolicus (Aa). Detailed Mössbauer studies of the C56S mutant of the Cp system revealed a mixture of clusters with valence-localized S = 1/2 and valence-delocalized S = 9/2 ground states. We relied on crystallographic structures of wild-type and mutant Aa Fd's in order to explain such a distribution of spin states.