An investigation of the first-order spin-state transition in Fe(Phen)(2)(NCS)(2) EXAFS and infrared spectroscopy

The structure of Fe(Phen)(2)(NCS)(2) has been examined across the first-order spin-state transition by EXAFS with full multiple scattering analysis. The EXAFS data at 298 K can be satisfactorily assigned to the high-spin state, but the analysis of the low-temperature data at 90 K is not entirely unequivocal, although consistent with the predominant presence of the low-spin state. That some proportion of the high-spin state remains at low temperatures, well below the first-order transition, is clearly evidenced in the infrared spectra, suggesting possible sublattice ordering.

Neutron diffraction study of the coupling between spin, lattice, and structural degrees of freedom in 0.8BiFeO(3)-0.2PbTiO(3)

A powder neutron diffraction study was carried out on 0.8BiFeO(3)-0.2PbTiO(3) in the temperature range 27-1000 degrees C. The system exhibits magnetic transition at similar to 300 degrees C and a rhombohedral (R3c)-cubic (Pm3m) ferroelectric phase transition at similar to 650 degrees C. Anomalous variation in the lattice parameters and the octahedral tilt angle is observed across the magnetic transition temperature. In the magnetic phase, the c parameter is contracted and the octahedral tilt angle is slightly increased. The results suggest coupling between the spin, lattice and structural degrees of freedom. (C) 2011 American Institute of Physics. doi:10.1063/1.3555093]

Magnetic and spin evolution of pulsars

We explore the consequences of the model of spin-down-induced flux expulsion for the magnetic field evolution in solitary as well as in binary neutron stars. The spin evolution of pulsars, allowing for their field evolution according to this model, is shown to be consistent with the existing observational constraints in both low- and high-mass X-ray binary systems. The contribution from pulsars recycled in massive binaries to the observed excess in the number of low-field (10(11)-10(12) G) solitary pulsars is argued to be negligible in comparison with that of normal pulsars undergoing a 'restricted' field decay predicted by the adopted field decay model. Magnetic fields of neutron stars born in close binaries with intermediate- or high-mass main-sequence companions are predicted to decay down to values as low as similar to 10(6) G, which would leave them unobservable as pulsars during most of their lifetimes. The post-recycling evolution of some of these systems can, however, account for the observed binary pulsars having neutron star or massive white dwarf companions. Pulsars recycled in the disc population low-mass binaries are expected to have residual fields greater than or similar to 10(8) G, while for those processed in globular clusters larger residual fields are predicted because of the lower field strength of the neutron star at the epoch of binary formation. A value of tau similar to 1-2 x 10(7) yr for the mean value of the Ohmic decay time-scale in the crusts of neutron stars is suggested, based on the consistency of the model predictions with the observed distribution of periods and magnetic fields in the single and binary pulsars.

On the dual head-discharge characteristics of a modified chimney weir

This paper is concerned with the dual head-discharge characteristics of a modified chimney weir. It is shown by an optimization procedure that the modified chimney weir having an inward trapezoidal weir over an inverted V-notch can produce discharges proportional to both the logarithm of the head as well as the linear power of the head reckoned independently over two different reference planes, within a prefixed maximum allowable percentage error from the theoretical discharge. A new technique is adopted to optimize the weir parameters, in order to obtain the maximum ranges of measurement under logarithmic, linear as well as combined characteristics. In the case of linear weir it is shown that it is possible to enhance the linearity range of the chimney weir by more than 540% and for a weir with constant indication accuracy by more than 350%. In addition, about 86% of the overall depth of the designed linear weir and over 90% of the logarithmic weir is converted as the corresponding measurable ranges. Experiments with four typical weirs give consistent constant average coefficient of discharge for each weir confirming the theory. The practical application of the weir in minor irrigation, hydraulic and other engineering fields is highlighted.

Role of free valences and spin densities on the migrating atom in location of saddle points in radical-exchange reactions

The principle of the conservation of bond orders during radical-exchange reactions is examined using Mayer's definition of bond orders. This simple intuitive approximation is not valid in a quantitative sense. Ab initio results reveal that free valences (or spin densities) develop on the migrating atom during reactions. For several examples of hydrogen-transfer reactions, the sum of the reaction coordinate bond orders in the transition state was found to be 0.92 +/- 0.04 instead of the theoretical 1.00 because free valences (or spin densities) develop on the migrating atom during reactions. It is shown that free valence is almost equal to the square of the spin density on the migrating hydrogen atom and the maxima in the free valence (or spin density) profiles coincide (or nearly coincide) with the saddle points in the corresponding energy profiles.

Density-matrix renormalization-group studies of the spin-1/2 Heisenberg system with dimerization and frustration

Using the density-matrix renormalization-group technique, we study the ground-state phase diagram and other low-energy properties of an isotropic antiferromagnetic spin-1/2 chain with both dimerization and frustration, i.e., an alternation delta of the nearest-neighbor exchanges and a next-nearest-neighbor exchange J(2). For delta = 0, the system is gapless for J(2) < J(2c) and has a gap for J(2) > J(2c) where J(2c) is about 0.241. For J(2) = J(2c) the gap above the ground state grows as delta to the power 0.667 +/- 0.001. In the J(2)-delta plane, there is a disorder line 2J(2) + delta = 1. To the left of this line, the peak in the static structure factor S(q) is at q(max) = pi (Neel phase), while to the right of the line, q(max) decreases from pi to pi/2 as J(2) is increased to large values (spiral phase). For delta = 1, the system is equivalent to two coupled chains as on a ladder and it is gapped for all values of the interchain coupling.

Enhanced charge and spin currents in the one-dimensional disordered mesoscopic Hubbard ring

We consider a one-dimensional mesoscopic Hubbard ring with and without disorder and compute charge and spin stiffness as a measure of the permanent currents. For finite disorder we identify critical disorder strength beyond which the charge currents in a system with repulsive interactions are larger than those for a free system. The spin currents in the disordered repulsive Hubbard model are enhanced only for small U, where the magnetic state of the system corresponds to a charge-density wave pinned to the impurities. For large U, the state of the system corresponds to localized isolated spins and the spin currents are found to be suppressed. For the attractive Hubbard model we find that the charge currents are always suppressed compared to the free system at all length scales.

Theoretical studies of the spin states of macrocyclic aza-amido binuclear copper (II) complexes

The spin and charge excitation gaps and charge and spin density distributions have been studied in macrocyclic binuclear aza-amido copper (II) complexes employing a model Hamiltonian. The spin gaps depend on the σ-orbital occupancies, and for small gaps, the exchange integral between the σ orbitals of the bridging oxygen atoms, KOO, which is sensitive to geometry, determines the low-lying spin excitations. The singlet—singlet gaps also depend upon the σ-orbital occupancy but are weakly dependent upon KOO.

Triple resonance, triple-quantum NMR studies of dipolar coupled spin systems

Multiple quantum-single quantum correlation experiments are employed for spectral simplification and determination of the relative signs of the couplings. In this study, we have demonstrated the excitation of three nuclei, triple quantum coherences and discussed the information obtainable from such experiments. The experiments have been carried out on doubly labeled acetonitrile and fluoroacetonitrile aligned in liquid crystalline media. The experiment is advantageous in providing many spectral parameters from a single experiment. The coherence pathways involved in the pulse sequence are described using product operators. (C) 2011 Elsevier Inc. All rights reserved.

Interplay of spin and lattice degrees of freedom in the frustrated antiferromagnet CdCr2O4: High-field and temperature-induced anomalies of the elastic constants

Temperature and magnetic field studies of the elastic constants of the chromium spinel CdCr2O4 show pronounced anomalies related to strong spin-phonon coupling in this frustrated antiferromagnet. A detailed comparison of the longitudinal acoustic mode propagating along the 111] direction with a theory based on an exchange-striction mechanism leads to an estimate of the strength of the magnetoelastic interaction. The derived spin-phonon coupling constant is in good agreement with previous determinations based on infrared absorption. Further insight is gained from intermediate and high magnetic field experiments in the field regime of the magnetization plateau. The role of the antisymmetric Dzyaloshinskii-Moriya interaction is discussed.

Spin-Selective Correlation Experiment for Measurement of Long-Range J Couplings and for Assignment of (R/S) Enantiomers from the Residual Dipolar Couplings and DFT

We report the C-HETSERF experiment for determination of long- and short-range homo- and heteronuclear scalar couplings ((n)J(HH) and (n)J(XH), n >= 1) of organic molecules with a low sensitivity dilute heteronucleus in natural abundance. The method finds significant advantage in measurement of relative signs of long-range heteronuclear total couplings in chiral organic liquid crystal. The advantage of the method is demonstrated for the measurement of residual dipolar couplings (RDCs) in enantiomers oriented in the chiral liquid crystal with a focus to unambiguously assign R/S designation in a 2D spectrum. The alignment tensor calculated from the experimental RDCs and with the computed structures of enantiomers obtained by DFT calculations provides the size of the back-calculated RDCs. Smaller root-mean-square deviations (rmsd) between experimental and calculated RDCs indicate better agreement with the input structure and its correct designation of the stereogenic center.

Spin and charge density waves in the extended Hubbard model: A slave-boson approach

We use the extended Hubbard model to investigate the properties of the charge- and spin-density-wave phases in the presence of a nearest-neighbors repulsion term in the framework of the slave-boson technique. We show that, contrary to Hartree-Fock results, an instablity may occur for sufficiently high values of the Hubbard repulsion, both in the spin- and charge-density-wave phase, which makes the system discontinuously jump to a phase with a smaller or zero wave amplitude. The limits of applicability of our approach are discussed and our results are compared with previous numerical analysis. The phase diagram of the model at half-filling is determined.

Spin state and exchange in the quasi-one-dimensional antiferromagnet KFeS2

We report the optical spectra and single crystal magnetic susceptibility of the one-dimensional antiferromagnet KFeS2. Measurements have been carried out to ascertain the spin state of Fe3+ and the nature of the magnetic interactions in this compound. The optical spectra and magnetic susceptibility could be consistently interpreted using a S = 1/2 spin ground state for the Fe3+ ion. The features in the optical spectra have been assigned to transitions within the d-electron manifold of the Fe3+ ion, and analysed in the strong field limit of the ligand field theory. The high temperature isotropic magnetic susceptibility is typical of a low-dimensional system and exhibits a broad maximum at similar to 565 K. The susceptibility shows a well defined transition to a three dimensionally ordered antiferromagnetic state at T-N = 250 K. The intra and interchain exchange constants, J and J', have been evaluated from the experimental susceptibilities using the relationship between these quantities, and chi(max), T-max, and T-N for a spin 1/2 one-dimensional chain. The values are J = -440.71 K, and J' = 53.94 K. Using these values of J and J', the susceptibility of a spin 1/2 Heisenberg chain was calculated. A non-interacting spin wave model was used below T-N. The susceptibility in the paramagnetic region was calculated from the theoretical curves for an infinite S = 1/2 chain. The calculated susceptibility compares well with the experimental data of KFeS2. Further support for a one-dimensional spin 1/2 model comes from the fact that the calculated perpendicular susceptibility at 0K (2.75 x 10(-4) emu/mol) evaluated considering the zero point reduction in magnetization from spin wave theory is close to the projected value (2.7 x 10(-4) emu/mol) obtained from the experimental data.

Spin distributions in antiferromagnetically coupled Mn2+Cu2+ systems: from the pair to the infinite chain

Probably the most informative description of the ground slate of a magnetic molecular species is provided by the spin density map. Such a map may be experimentally obtained from polarized neutron diffraction (PND) data or theoretically calculated using quantum chemical approaches. Density functional theory (DFT) methods have been proved to be well-adapted for this. Spin distributions in one-dimensional compounds may also be computed using the density matrix renormalization group (DMRG) formalism. These three approaches, PND, DFT, and DMRG, have been utilized to obtain new insights on the ground state of two antiferromagnetically coupled Mn2+Cu2+ compounds, namely [Mn(Me-6-[14]ane-N-4)Cu(oxpn)](CF3SO3)(2) and MnCu(pba)(H2O)(3) . 2H(2)O, with Me-6-[14]ane-N-4 = (+/-)-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane, oxpn = N,N'-bis(3-aminopropyl)oxamido and pba = 1,3-propylenebis(oxamato). Three problems in particular have been investigated: the spin distribution in the mononuclear precursors [Cu(oxpn)] and [Cu(pba)](2-), the spin density maps in the two Mn2+Cu2+ compounds, and the evolution of the spin distributions on the Mn2+ and Cu2+ sites when passing from a pair to a one-dimensional ferrimagnet.