Equilibrium properties of a spin-1 Ising system with bilinear,biquadratic and odd interactions

The equilibrium properties of the spin-1 Ising system Hamiltonian with arbitrary bilinear (J), biquadratic (K) and odd (L), which is also called dipolar-quadrupolar, interactions is studied for zero magnetic field in the lowest approximation of the cluster variation method. The odd interaction is combined with the bilinear (dipolar) and biquadratic (quadrupolar) exchange interactions by the geometric mean. In this system, phase transitions depend on the ratio of the coupling parameters, α = J/K; therefore, the dependence of the nature of the phase transition on α is investigated extensively and it is found that for α ⩽ 1 and α ⩾ 2000 a second-order phase transition occurs, and for 1 < α < 2000 a first-order phase transition occurs. The critical temperatures in the case of a second-order phase transition and the upper and lower limits of stability temperature in the case of a first-order phase transition are obtained for different values of α calculated using the Hessian determinant. The first-order phase transition temperatures are found by using the free energy values while increasing and decreasing the temperature. Besides the stable branches of the order parameters, we establish also the metastable and unstable parts of these curves and the thermal variations of these solutions as a function of the reduced temperature are investigated. The unstable solutions for the first-order phase transitions are obtained by displaying the free energy surfaces in the form of a contour map. Results are compared with the spin-1 Ising system Hamiltonian with the bilinear and biquadratic interactions and it is found that the odd interaction greatly influences the phase transitions.     

Low-temperature spectrum and damping of elementary excitations in biquadratic exchange systems (S = 1)

The diagrammatic technique for the standard basis operators and the expansion in powers of 1/z (where z is the number of spins interacting with any given spin) are used to calculate the energies of magnons (in the ferromagnetic and quadrupolar phases) and quadrons (in the ferromagnetic phase) and the bipolar and quadrupolar order parameters (in both phases) in the (1/z)¹ approximation and at low temperatures. it is shown that magnons are damped with the exception of the (ferromagnetic and quadrupolar) case of the Schrödinger exchange model and quadrupolar phase; the quadrons are undamped only in a special case of the ferromagnetic phase, i.e. in the ferrogmatic case of the Schrödinger exchange model. In the limit K → 0, i.e. the biquadratic exchange interaction tends to zero, the spectrum of magnons and their damping are identical with the results by Balakhonov et al. The spin waves and quadrupolar order parameter are discussed in more detail in the following cases of the quadrupolar phase: ferromagnetic-quadrupolar limit, isotropic purely quadrupolar interactions, and quadrupolar-antiferromagnetic limit.     

Non-equilibrium relaxation study of the ±J Ising model with biquadratic exchange interaction

The spin-1 ±J Ising model with uniform biquadratic couplings on a simple cubic lattice is studied by the Monte Carlo simulation using the non-equilibrium relaxation method. The reentrant phase transition induced by competition between the bilinear and biquadratic couplings is eliminated gradually with increasing randomness of bilinear couplings and disappears entirely in the strong random system. The dynamic exponent of ferromagnetic transition shows non-universal behavior with changing randomness, while this behavior is not observed in the case of staggered quadrupolar transition.     

Quadrupole relaxation enhancement--application to molecular crystals

A general theory of field dependent spin-lattice relaxation for nuclei of the spin quantum number 1/2 (1H, 19F, 13C) caused by dipole-dipole interactions with neighboring quadrupolar nuclei (nuclei possessing a quadrupolar moment) is presented. The theory is valid for arbitrary motional conditions and should be treated as a quadrupolar counterpart of the paramagnetic relaxation enhancement theory. When the energy level splitting of the dipolar spin (I=1/2) matches one of the transition frequencies of the quadrupolar nuclei one can observe a local enhancement of the dipolar spin relaxation (referred to as "quadrupolar peaks"). To see such effects the dynamics modulating the spin interactions has to be relatively slow. This brings the system beyond the validity range of perturbation approaches and requires the stochastic Liouville equation to be applied. The presented theory describes the quadrupolar relaxation enhancement (QRE) for an arbitrary spin quantum number of the quadrupolar nuclei and includes the asymmetry of the quadrupolar coupling. It has been applied to interpret the shape of magnetization curves (amplitude of 1H magnetization versus magnetic field) for the molecular crystal [C3N2H5]6[Bi4Br18] ([C3N2H5]-imidazolium). The magnetization curves show several dips (local minima) attributed to 1H-14N quadrupolar relaxation enhancement effects. In addition, as a limiting case a perturbation approach to QRE has been presented and its validity conditions have been discussed.     

Influence of magnetic dipole and magnetoelastic interactions on the phase states of 2D non-Heisenberg ferromagnetic with complex exchange interactions

The phase states of the 2D non-Heisenberg ferromagnetic with anisotropic bilinear and biquadratic exchange interactions are investigated. The limiting cases of the system under consideration are the two-dimensional XY-model with biquadratic exchange interaction and the isotropic Heisenberg ferromagnetic. The account of the magnetic dipole interaction leads to the realization of spatially inhomogeneous quadrupolar phase. The stability regions of various phase transitions for different values of the material parameters are studied. The phase diagram is built. Besides, the temperature phase transitions are investigated. The influence of the magnetoelastic interaction on the formation of the long-range quadrupolar order is determined.     

Geometry of kinked protein helices from NMR data

Residual dipolar couplings between spin-1/2 and quadrupolar nuclei are often observed and exploited in the magic-angle spinning (MAS) NMR spectra of spin-1/2 nuclei. These orientation-dependent splittings contain information on the dipolar interaction, which can be translated into structural information. The same type of splittings may also be observed for pairs of quadrupolar nuclei, although information is often difficult to extract from the quadrupolar-broadened lineshapes. Here, the complete theory for describing the dipolar coupling between two quadrupolar nuclei in the frequency domain by Hamiltonian diagonalization is given. The theory is developed under MAS and double-rotation (DOR) conditions, and is valid for any spin quantum numbers, quadrupolar coupling constants, asymmetry parameters, and tensor orientations at both nuclei. All terms in the dipolar Hamiltonian become partially secular and contribute to the NMR spectrum. The theory is validated using experimental 11B and 35/37Cl NMR experiments carried out on powdered B-chlorocatecholborane, where both MAS and DOR are used to help separate effects of the quadrupolar interaction from those of the dipolar interaction. It is shown that the lineshapes are sensitive to the quadrupolar coupling constant of both nuclei and to the J coupling (including its sign). From these experiments, the dipolar coupling constant for a heteronuclear spin pair of quadrupolar nuclei may be obtained as well as the sign of the quadrupolar coupling constant of the perturbing nucleus; these are two parameters that are difficult to obtain experimentally otherwise.     

Magnetic relaxation in a spin-1 Ising model near the second-order phase transition point

The magnetic relaxation of a spin-1 Ising model with bilinear and biquadratic interactions is formulated within the framework of statistical equilibrium theory and the thermodynamics of irreversible processes. Using a molecular-field expression for the magnetic Gibbs energy, the magnetic Gibbs energy produced in the irreversible process is calculated and time derivatives of the dipolar and quadrupolar order parameters are treated as fluxes conjugate to their appropriate generalized forces in the sense of Onsager theory. The kinetic equations are obtained by introducing kinetic coefficients that satisfy the Onsager relation. By solving these equations an expression is derived for the dynamic or complex magnetic susceptibility. From the real and imaginary parts of this expression, magnetic dispersion and absorption factor are calculated and analyzed near the second-order phase transition.     

Li NMR in lithium borate glasses

In anticipation of using fluctuations in the nuclear dipolar and quadrupolar interaction as a probe of lithium ion motion in lithium borate glasses, the static values of these interactions were measured using a variety of echo techniques. The static quadrupolar echo spectrum of ⁷Li and a calculation of the dipolar interaction in crystalline Li₂B₄O₇ (same chemical composition as the glass under study) were used to estimate the strength of the two interactions. These indicate that the dipolar and quadrupolar interactions for ⁶Li will be of similar size and the dipolar interaction will be dominated by the unlike spin interaction between the ⁶Li and the ¹⁰B, ¹¹B spins. An appropriate theoretical model is proposed and explicit expressions for the echo amplitude are calculated in terms of the dipolar and quadrupolar second moments. This single spin model takes into account the quadrupolar interaction but treats the dipolar interaction as an effective magnetic field. Experimental results are presented which show the essential validity of the model and measurements lead to reasonable values for the dipolar and quadrupolar second moments. The relative merits of the various echo techniques are discussed.     

6Li NMR in lithium borate glasses

In anticipation of using fluctuations in the nuclear dipolar and quadrupolar interaction as a probe of lithium ion motion in lithium borate glasses, the static values of these interactions were measured using a variety of echo techniques. The static quadrupolar echo spectrum of ⁷Li and a calculation of the dipolar interaction in crystalline Li₂B₄O₇ (same chemical composition as the glass under study) were used to estimate the strength of the two interactions. These indicate that the dipolar and quadrupolar interactions for ⁶Li will be of similar size and the dipolar interaction will be dominated by the unlike spin interaction between the ⁶Li and the ¹⁰B, ¹¹B spins. An appropriate theoretical model is proposed and explicit expressions for the echo amplitude are calculated in terms of the dipolar and quadrupolar second moments. This single spin model takes into account the quadrupolar interaction but treats the dipolar interaction as an effective magnetic field. Experimental results are presented which show the essential validity of the model and measurements lead to reasonable values for the dipolar and quadrupolar second moments. The relative merits of the various echo techniques are discussed.     

Dipolar and quadrupolar detection using an FT-ICR MS setup at the MPIK Heidelberg

Dipolar and single-phase two-electrode quadrupolar detection schemes have been investigated at a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) setup built for the KATRIN experiment at the Max-Planck-Institute for Nuclear Physics (MPIK) in Heidelberg. We present first experimental results of ⁷Li^?+? signals from a cylindrical Penning trap configuration for both detection schemes. While the prominent signal of the conventional dipolar detection scheme marks the reduced cyclotron frequency, the main signal for the quadrupolar detection appears at the sum of the reduced cyclotron frequency and the magnetron frequency. For ideal trapping fields, this sum frequency equals the ion cyclotron frequency ?? _c ?=?qB/(2??m). Sidebands due to the combined motions of the cyclotron mode and magnetron mode are observed by quadrupolar detection which allows the determination of the respective combinations of eigenfrequencies.     

The application of the differential operator method to the Blume-Emery-Griffiths model

Within an effective-field approximation, general expressions for evaluating the second-order phase transition line and the tricritical point of the anisotropic Blume-Emery-Griffiths model are obtained by the use of the differential operator technique. The phase diagrams and the behavior of the tricritical point are investigated numerically for the honeycomb lattice (z = 3) and square lattice (z = 4). We find a new disordered phase which may correspond to the staggered quadrupolar phase predicted in the Monte Carlo simulation, when some conditions are satisfied. The phase diagrams for z = 3 and z = 4 systems exhibit a reentrant behavior for positive values of the uniaxial anisotropy parameter. The change of the tricritical point with the value of the reduced biquadratic parameter is also studied for the system with z = 3.     

A spin-one Ising model on the Bethe lattice

We study the statistical mechanics of spin-one Ising models on the Bethe lattice assuming that the spins interact by dipolar and quadrupolar interactions. An exact calculation of the properties of the system is performed on the basis of the general formulation of Morita. An exact expression for the Curie temperature is derived and the results are found to be in agreement with those of Obokata and Oguchi who utilized a generalized Bethe approximation to a spin-one Ising system. The nature of variation of the Curie temperature with respect to the change of quadrupolar exchange is discussed for various coordination numbers and the results agree qualitatively with the earlier works. The temperature variation of both dipolar and quadrupolar moments is studied.     

HYSCORE analysis of nitrogen hyperfine interactions

A semiquantitative treatment of hyperfine sublevel correlation spectra of aS=1/2,I=1 spin system is presented. The derived closed analytical expressions allow the determination of components of the dipolar and quadrupolar coupling tensors. The method is applicable if nonsecular terms can be neglected and if canonical orientations of the hyperfine interactions can be selected via a dominantg matrix or hyperfine anisotropy.     

Rotor-encoded heteronuclear MQ MAS NMR spectroscopy of half-integer quadrupolar and spin I=1/2 nuclei

A new two-dimensional heteronuclear multiple-quantum magic-angle spinning (MQ MAS) experiment is presented which combines high resolution for the half-integer quadrupolar nucleus with information about the dipolar coupling between the quadrupolar nucleus and a spin I=1/2 nucleus. Homonuclear MQ coherence is initially created for the half-integer quadrupolar nucleus by a single pulse as in a standard MQ MAS experiment. REDOR recoupling of the heteronuclear dipolar coupling then allows the creation of a heteronuclear multiple-quantum coherence comprising multiple- and single-quantum coherence of the quadrupolar and spin I=1/2 nucleus, respectively, which evolves during t1. Provided that the t1 increment is not rotor synchronized, rotor-encoded spinning-sideband patterns are observed in the indirect dimension. Simulated spectra for an isolated IS spin pair show that these patterns depend on the recoupling time, the magnitude of the dipolar coupling, the quadrupolar parameters, as well as the relative orientation of the quadrupolar and dipolar principal axes systems. Spectra are presented for Na2HPO4, with the heteronuclear 23Na-1HMQ MAS experiments beginning with the excitation of 23Na (spin I=3/2) three-quantum coherence. Coherence counting experiments demonstrate that four- and two-quantum coherences evolve during t1. The heteronuclear spinning-sideband patterns observed for the three-spin H-Na-H system associated with the Na(2) site are analyzed. For an IS2 system, simulated spectra show that, considering the free parameters, the spinning-sideband patterns are particularly sensitive to only, first, the angle between the two IS internuclear vectors and, second, the two heteronuclear dipolar couplings. It is demonstrated that the proton localization around the Na(2) site according to the literature crystal structure of Na2HPO4 is erroneous. Instead, the experimental data is consistent with two alternative different structural arrangements, whereby either there is a deviation of 10 degrees from linearity for the case of two identical Na-H distances, or there is a linear arrangement, but the two Na-H distances are different. Furthermore, the question of the origin of spinning-sidebands in the (homonuclear) MQ MAS experiment is revisited. It is shown that the asymmetric experimental MQ sideband pattern observed for the low-C(Q) Na(2) site in Na(2)HPO4 can only be explained by considering the 23Na chemical shift anisotropy.     

Field-dependent nuclear relaxation of spins 1/2 induced by dipole-dipole couplings to quadrupole spins: LaF3 crystals as an example

A general theory of spin-lattice nuclear relaxation of spins I=1/2 caused by dipole-dipole couplings to quadrupole spins S1, characterized by a non-zero averaged (static) quadrupole coupling, is presented. In multispin systems containing quadrupolar and dipolar nuclei, transitions of spins 1/2 leading to their relaxation are associated through dipole-dipole couplings with certain transitions of quadrupole spins. The averaged quadrupole coupling attributes to the energy level structure of the quadrupole spin and influences in this manner relaxation processes of the spin 1/2. Typically, quadrupole spins exhibit also a complex multiexponential relaxation sensed by the dipolar spin as an additional modulation of the mutual dipole-dipole coupling. The proposed model includes both effects and is valid for an arbitrary magnetic field and an arbitrary quadrupole spin quantum number. The theory is applied to interpret fluorine relaxation profiles in LaF3 ionic crystals. The obtained results are compared with predictions of the 'classical' Solomon relaxation theory.     

Hysteretic behavior of quadrupolar ordering in a 2D magnetic spin˗1 Ising nanoparticle

Pair approximation technique has been used to study the quadrupolar ordering properties for the 2D magnetic spin-1 Ising nanoparticles, consisting of core and surface parts with an interface coupling. Similar to the magnetic hysteresis, it has been shown that the quadrupole order parameter (Q) as a function of single-ion anisotropy (D) has a ‘hysteresis’ character which is generally called quadrupole (or QD) hysteresis. The observed QD loops strongly depend on temperature (T), external magnetic field (H) and biquadratic exchange interaction (K). Shifted QD loops with an asymmetry are found when H and K values are increased. These behaviors are also discussed in relation to other theoretical findings.     

On biquadratic exchange interactions in spin-1 systems

It is showed rigorously that the spin-1 Ising-like Hamiltonian with biliniar and biquadratic exchange interactions and a Hamiltonian with uniaxial and biaxial quadrupolar pair interactions have exactly the same thermodynamic properties. Consequences of the theore, are discussed.     

Spin-locking and recoupling of homonuclear dipolar interaction between spin-3/2 nuclei under magic-angle sample spinning

Numerical simulations and experiments were used to examine the possibility of employing strong spin-lock fields for recoupling of homonuclear dipolar interactions between spin-3/2 quadrupolar nuclei and to compare it to the rotary-resonance recoupling at weak spin-lock fields. It was shown that strong spin-lock pulses under MAS conditions can lead to recoupling, provided that the electric-field gradient principal axes systems of the coupled nuclei are aligned and that their quadrupolar coupling constants are approximately the same. The phenomenon is based on the fact that strong spin-lock pulses induce adiabatic transfer of magnetization between the central-transition coherence and the triple-quantum coherence with equal periodicity as is the periodicity of the time-dependent dipolar coupling. Because of the synchronous variation of the state of the spin system and of the dipolar interaction, the effect of the latter on the central-transition coherence and on the triple-quantum coherence is not averaged out by sample rotation. The approach is, however, very sensitive to the relative orientation of the electric-field gradient principal axes systems and therefore less robust than the approach based on weak spin-lock pulses that satisfy rotary-resonance condition.     

Renormalization group approach to three-state spin models in two dimensions

The real space renormalization group approach is used to study spin one anisotropic models with dipolar and quadrupolar interactions on the triangular lattice. The method is tested for the three state Potts model and the Blume-Emery-Griffiths model leading to results which are basically in agreement with other treatments of these models. The phase diagram for a quadrupolar model (anisotropic Potts model) is obtained and the influence of an external magnetic field on the transition temperature to the quadrupolar phase is determined. The fixed point which controls a transition to the phase with Ising dipolar order andXY-type quadrupolar order is found.Work performed within the research program of the Sonderforschungsbereich 341, Köln-Aachen-Jülich     

Dipole-quadrupole force ratios determine the ability of potential models to describe the phase diagram of water

We show that, in order to yield an acceptable phase diagram for water, the key ingredient is the relative strength of the dipolar and quadrupolar forces. We also demonstrate that for three-point-charge water models the relative strength of the dipolar to quadrupolar forces is determined by the position of the negative charge. This provides a theoretical background--supported by the experiment--to our knowledge of the water interactions which at present is essentially dominated by empirical models. In addition, it can be quite useful in the development of improved water models with a more physical basis.