Ab initio modeling of the electronic and spin properties of the [NV]<Superscript>−</Superscript> centers in diamond nanocrystals

The electronic and spin properties of different nanocrystals of carbon are studied. The properties of these cluster systems are modeled in terms of the ab initio (Hartree-Fock) and semiempirical (PM3, AM1) quantum-chemical methods. The calculations are performed for different carbon nanocluster systems: defect-free and with [NV]^? centers, hydrogen passivated (C₃₈H₄₂, C₇₁H₈₄, C₈₆H₇₈), and with a free (unpassivated) surface (C₃₈, C₇₁, C₈₆). The spin properties of unhydrated nanoclusters were studied for the first time. The structure of all the clusters under study was optimized using the total energy minimization principle. It is shown that, in the case of hydrated carbon nanocrystals passivated by hydrogen atoms, diamond-like clusters are formed. The atomic structure of an unpassivated nanocrystal depends on the number of atoms in the cluster, as well as on its initial geometrical parameters. In some cases, clusters with a fullerene-like surface are formed. In hydrogenpassivated diamond nanocrystals with [NV]^? centers, the spin density is localized at the nuclei of C atoms nearest to the center vacancies. For the unpassivated counterparts, the spin density is localized at the nuclei of C atoms forming the surface of the corresponding nanocrystal.     

The transient EPR spectra and spin dynamics of coupled three-spin systems in photosynthetic reaction centres

The concept of introducing an additional, stable paramagnetic species into photosynthetic reaction centres to increase the information content of their spin polarized transient EPR spectra is investigated theoretically. The light-induced electron transfer in such systems generates a series of coupled three-spin states consisting of sequential photoinduced radical pairs coupled to the stable spin which acts as an “observer”. The spin polarized transient EPR spectra are investigated using the coupled three-spin system P⁺I⁻Q⁻ _A in pre-reduced bacterial reaction centres as a specific example which has been studied experimentally. The evolution of the spin system and the spin polarized EPR spectra of P⁺I⁻Q⁻ _A and Q⁻ _A following recombination of the radical pair (P = primary donor, I = primary acceptor, Q_A = quinone acceptor) are calculated numerically by solving the equations of motion for the density matrix. The net polarization of the observer spin is also calculated analytically by perturbation theory for the case of a single, short-lived, charge-separated state. The result bears a close resemblance to the chemically induced nuclear polarization (CIDNP) generated in photolysis reactions in which a nuclear spin plays the role of the observer interacting with the radical pair intermediates. However, because the Zeeman frequencies of the three electron spins involved are usually quite similar, the polarization of the electron observer spin in strong magnetic fields can reflect features of the CIDNP effect in both, high and low magnetic fields. The dependence of the quinone spin polarization on the exchange couplings in the three-spin system is investigated by numerical simulations, and it is shown that the observed emissive polarization pattern is compatible with either sign, positive or negative, for a range of exchange couplings, J_PI, in the primary pair. The microwave frequency and orientation dependence of the spectra are discussed as two of several possible criteria for determining the sign of J_PI.     

Exchange and dipolar spin-spin interaction and rotational diffusion in saturation transfer EPR spectroscopy

Saturation transfer EPR spectroscopy (STEPR) provides a means for investigating weak spin-spin interaction between spin-labelled molecules because the spectral intensity is proportional to the effective spin-lattice relaxation time,T ₁ ^eff. Rate equations for the spin population defferences yield equivalent results for the dependence ofT ₁ ^eff on the physical (or chemical) and Heisenberg spin exchange rates and show thatT ₁ ^eff depends on the extent of redistribution of saturation throughout the anisotropic spin label powder lineshape. This approach yields a particularly simple formulation for the dependence of the STEPR lineshape on slow rotational diffusion. The effects of spin exchange are readily distinguished from those of slow rotational diffusion because of the insensitivity of the STEPR lineshape in the former case. The characteristic dependence of the STEPR spectral intensity on spin concentration allows determination of the exchange rate and can be used for studying slow translational diffusion, e.g. of spin-labelled proteins. Dipolar relaxation induced by paramagnetic ions gives a linear dependence of the reciprocal spin label STEPR intensity on metal ion concentration. STEPR measurements with spin-labelled lipid molecules in gel phase membranes in the presence of Ni²⁺ ions yield reliable distance information and provide calibrations for use with other systems.     

Theoretical investigations of the spin Hamiltonian parameters and local tetragonal distortions for Cu2+ in crystalline and amorphous TeO2 and GeO2

The spin Hamiltonian parameters (i.e., anisotropic g factors and hyperfine structure constants) and local tetragonal distortions for Cu²⁺ in crystalline and amorphous TeO₂ and GeO₂ are theoretically investigated using the high-order perturbation formulas of these parameters for a tetragonally elongated octahedral 3d⁹ cluster. The impurity Cu²⁺ occupying the octahedral sites are found to experience the relative tetragonal elongation ratios of about 11.4% and 9.5% for crystalline TeO₂ and GeO₂ and 10.8% and 6.6% for amorphous TeO₂ and GeO₂, respectively, along the C₄ axis due to the Jahn–Teller effect. This reveals the larger tetragonal elongation distortions for the Cu²⁺ centres in crystalline than amorphous systems (especially TeO₂). The theoretical spin Hamiltonian parameters show good agreement with the experimental data. The results are discussed.     

The thermodynamic limit for long-range random systems

Long-range spin systems with random interactions are considered. A simple argument is presented showing that the thermodynamic limit of the free energy exists and depends neither on the specific random configuration nor on the sample shape, provided there is no external field. The argument is valid for both classical and quantum spin systems, and can be applied to (a) spins randomly distributed on a lattice and interacting via dipolar interactions; and (b) spin systems with potentials of the formJ(x ₁,x ₂)/|x ₁ -x ₂| ^αd , where theJ(x ₁,x ₂) are independent random variables with mean zero,d is the dimension, and α > 1/2. The key to the proof is a (multidimensional) subadditive ergodic theorem. As a corollary we show that, for random ferromagnets, the correlation length is a nonrandom quantity.     

Ferromagnetic half-metallic characteristic in bulk Ni0.5M0.5O (M=Cu,Zn and Cd): A GGA+U study

Ferromagnetic half metallicity with a high spin polarization of 100% was predicted in the bulk Ni_0.5Cu_0.5O using density-functional theory method. The band gap of majority spin is 3.45 eV for Ni_0.5Cu_0.5O. The density of states of minority spin at the Fermi level are mainly from Cu 3d and O 2p in the Ni_0.5Cu_0.5O. The magnetic moments are from Ni 3d states. Ni_0.5Zn_0.5O and Ni_0.5Cd_0.5O systems are ferromagnetic insulators, but the magnetic moment of Ni²⁺ ions is enhanced by the Zn and Cd incorporation. Therefore, Ni_0.5Cu_0.5O is the potential candidate for spintronics devices because of the predicted high spin polarization.     

Structure and magnetism of iron-sulfur clusters in proteins

Iron-sulfur clusters are mixed-valence systems exhibiting both localized and delocalized valence states. We discuss here spin-coupling models for two types of oxidized [3Fe-4S] clusters with localized Fe³⁺ valence states; a Heisenberg Hamiltonian with isotropic antiferromagnetic exchange fits the data well. Reduced [3Fe-4S] clusters, on the other hand, contain a trapped Fe³⁺ site and a delocalized Fe³⁺-Fe²⁺ pair. The pair has spin S₁₂=9/2 (formally ferromagnetic coupling) and is antiferromagnetically coupled to the Fe³⁺ S₃=5/2 spin to yield a system spin S=2. We discuss also recent results for [4Fe-4S] clusters such as [3Fe-4S]→[4Fe-4S] conversions, incorporation of other metals into the iron-sulfur core, and the observation of novel spin states.     

Coherent Exchange Cluster Approach for two-dimensional disordered Heisenberg spin systems

The spin wave properties of disordered two-dimensional and quasi two-dimensional Heisenberg spin systems, with an antiferromagnetic ground state (Neèl state) induced by single-ion anisotropy, are discussed within a Coherent Exchange Cluster Approach (Cluster CEA).The configuration averaged Green's functions are described by an effective spin wave Hamiltonian, with two sets of complex and energy dependent coherent exchange integralsJ _lm ¹ (E) andJ _lm ² (E) appropriate to the consideration of two different spins of the binary alloy constituents.J _lm ¹ andJ _lm ² , depending only on the distance of the sitesl andm, are taken to be non zero only for nearest neighbours. The remaining two quantitiesJ ¹(E) andJ ²(E) are determined self-consistently from the requirement that the most important matrix elements of the scatteringT matrix vanish when the configuration averaging has been performed.Numerical results are presented for the antiferromagnetic quasi two-dimensional systems K₂Ni _c Mn_1-c F₄ and Rb₂Fe _c Mn_1-c F₄.Both the density of states and the transverse susceptibilities, determining essentially the neutron scattering cross-sections, are calculated.The density of spin wave states for K₂Ni _c Mn_1-c F₄ is compared for different concentrations with exact computer calculations for finite 30 × 30 arrays. The agreement is excellent.Based on the thesis of H.J. Schlichting, Fachbereich Physik der Universität Hamburg, 1974.     

Molecular magnetism in closo-azadodecaborane supericosahedrons

ABSTRACT

The connection of 12 s = ½ closo-azadodecaborane radical units (NB₁₁H₁₁?), where a hydrogen atom is removed from the nitrogen atom, produces a supericosahedron [(NB₁₁H₆?)₁₂]^(S), S being the total spin of the system. This work describes the study of the low-lying energy spin-projected states of this supericosahedron with two different geometrical arrangements, each nitrogen atom pointing (1) inwards or (2) outwards with respect to radial axes. These spin-projected states are mapped into a Heisenberg spin Hamiltonian, thus allowing the determination of coupling constants between magnetic sites. The eigenvalues of this model Hamiltonian then predict the ground spin state and the corresponding combinations of spin orientations of the magnetic centres. We show that the energy minimum in the [(N_in/outB₁₁H₆?)₁₂]^(S) systems corresponds to a high-spin S = 6 state.     

Improved J-Compensated Apt Experiments

The derivation and investigation of two new J-compensated attached-proton-test experiments, CAPT2 and CAPT3, are presented. These methods incorporate fewer pulses than CAPT and are shown to be more effective over a wider range of ¹J_CH than spin flip, APT, and CAPT for CH, CH₂, and CH₃ spin systems. In addition, the magnitude of the flip angle of the initial pulse which creates transverse carbon magnetization is unrestricted in CAPT2 and CAPT3. The compensated CAPT3 sequence, which is patterned after the 90°_x90°_y90°_x composite pulse, is found to be excellent for routine use in ¹³C spectroscopy.     

A frequency-selective REDOR experiment for an SI2 spin system

A frequency-selective REDOR experiment is described for SI₂ spin systems. The experiment causes the net dipolar dephasing of the S spin to evolve only under the influence of one of the I spins. The experiment is based on a single pair of appropriately phased 90° I-spin pulses, and the I spin causing the S-spin dipolar dephasing is determined by the relative phases between the two 90° pulses. The experiment is demonstrated on a sample of ¹⁵N₂-l-asparagine.     

Spin glasses with short range interaction

The theory is presented of spin glasses for which the condition n _m ^1/3 l « dl is valid, l being the range of interaction forces between spins and n _m the volume concentration of spins. Various examples where such an interaction appears are considered. Thermodynamic and kinetic characteristics of such systems are calculated at high and low temperatures. Particular attention is paid to the transition region; for its analysis percolation theory methods are applied. The theory of one-dimensional spin glasses of several types is constructed. A ‘kinetic’ equation is derived for the cluster distribution function in the transition region and the behaviour of this function is studied.     

Effect of Viscosity on the Spin Exchange of TCNE and TEMPO Radicals with Iron(III) Acetylacetonate

The spin exchange of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and the radical anion of tetracyanoethene (TCNE), with iron acetylacetonate, Fe(acac)₃, was investigated as a function of solvent viscosity and temperature by X-band EPR spectroscopy. Acetone, methanol, ethanol, 1-propanol, 1-pentanol, 1-hexanol, 1-octanol, and chloroform were used as solvents because they provide a wide range of viscosity. The spin exchange rate constants measured in the different solvents ranged from 3 × 10⁸ to 8 × 10⁹ M⁻¹ s⁻¹, and from 7 × 10⁸ to 1 × 10¹⁰ M⁻¹ s⁻¹ for the TEMPO/Fe(acac)₃ and the TCNE/Fe(acac)₃ systems, respectively. The spin exchange rate constants, k _e, are compared with the corresponding diffusion rate constants. It was found that the k _e values correlate well with those of diffusion and hence the intermolecular spin exchange is strongly diffusion-controlled. The activation energies and pre-exponential factors are calculated from the Arrhenius plots.     

Analysis of the sequence of insulator-metal phase transitions at high pressure in systems with spin crossovers

Possible variants of the Mott-Hubbard phase transitions at high pressure in systems with spin crossovers are considered. Owing to the universal character of the dependence of the effective Hubbard parameter U _eff(d ⁿ ) on the average number of d electrons, which is determined by the presence of spin crossovers, cascades of insulator-metal-insulator phase transitions in systems with d ³, d ⁶, and d ⁸ configurations become possible. Moreover, the systems with d ⁶ configuration can exhibit transitions from a metal in the absence of external pressure to an insulator at high pressure.     

Magnetic properties of high-T c superconductors from NQR and NMR measurements

NMR and NQR spectra and spin-lattice relaxation measurements carried out in LASCO and YBCO-type crystals are presented and analyzed in order to derive insights on the correlations and spin-dynamics of the Cu²⁺ ions and on the microscopic mechanisms of high-T _c superconductivity. As an illustrative example on how the magnetic correlation length and spin dynamics properties can be extracted from the relaxation rateW, the³⁵Cl NMR data in the two-dimensional Heisenberg system Sr₂CuCl₂O₂, around the paramagnetic-antiferromagnetic (PA-AF) transition are first considered. Then the¹³⁹La NQR relaxation measurements in La_2?xSr_xCuO₄ are briefly reviewed and it is shown how a simple picture of localized Cu²⁺ magnetic moments, whose spin fluctuation times are controlled by the charge defects induced by the doping, leads in a direct way to quantitative estimates for the progressive shift, on cooling, of the spectral density of the low-frequency spin excitations towards the high frequency range. This phenomenon can be described in terms of effective spin at the Cu²⁺ ions, and its similarities with the analogous effect of progressive delocalization in Heavy Fermions systems are pointed out. Thus, the superconducting transition appears to occur in an unconventional Fermi liquid with AF correlations among itinerant pseudoparticles, possibly involving a mechanism not directly related to the magnetic correlated dynamics. In fact, a universal behavior of the relaxation rates as a function of temperature is observed, regardless of the transition temperatureT _c. The independence ofT _c from the low frequency static and dynamical spin properties is also indicated by⁸⁹Y Knight shifts and from⁶³Cu relaxation rates in systems like YBa₂Cu₄O₈ (Y124), whereT _c can be changed by atomic substitutions and by controlling the oxygen stoichiometry. The effect of an external magnetic field on the correlated spin dynamics of the AF Fermi liquid is investigated and from a comparison of Cu NQR relaxation and NMR relaxation in oriented powder of YBCO and LASCO it is shown that the external field has the small but unambiguous effect of depressing the relaxation rates aboveT _c, besides strongly enhancing them in the superconducting phase. A maximum in the ratio \({{W\left( {NQR} \right)} \mathord{\left/ {\vphantom {{W\left( {NQR} \right)} {W\left( {\vec H\left\| {\vec c} \right.} \right)}}} \right. \kern-0em} {W\left( {\vec H\left\| {\vec c} \right.} \right)}}\) is thus observed around 80 K, either in LASCO or in YBCO, again indicating that the transition could be driven by a mechanism not directly involving the spin dynamic properties. To study the role of the fluxions belowT _c ⁸⁹Y NMR shifts and spectra in oriented powders of YBCO are analyzed. Information on the spin susceptibility and on the structure of the vortex lattice is obtained. In addition, from the temperature behavior of the linewidth a motional narrowing related to flux melting is evidenced. The effective correlation time for the vortex motion is derived and it is discussed why μ⁺SR cannot detect it in view of the different rigid-lattice line broadening.     

EPR Study of Sc<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Nd<Superscript>143</Superscript> 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.     

Proton Exchange Effects in Laser Photolystic P-Benzosemiquinone Spin Polarized Radicals

The TRESR spectra of benzosemiquinone radical and the ethylene glycoi ketyl radical formed from laser photolysis of P-benzoquinone in ethylene glycoi or ethylene glycol/water systems are presented. The photon exchange between p-benzosemiquinone radicals PBQH⁺ and their protonated forms PBQH⁺ is studied by adding H₂SO₄ to the solution. The experimental results show that different hyperfine lines for PBQH⁺ have different time-dependence which depend upon the fraction of the overall number of nuclear spin states, and that the lines with smaller fraction are decay fast.