Theory of chemical bonds in metalloenzymes XX: magneto-structural correlations in the CaMn4O5 cluster in oxygen-evolving complex of photosystem II

ABSTRACT

Magneto-structural correlations in oxygen-evolving complex (OEC) of photosystem II (PSII) have been elucidated on the basis of theoretical and computational results in combination with available electron paramagnetic resonance (EPR) experimental results, and extended x-ray absorption fine structure (EXAFS) and x-ray diffraction (XRD) results. To this end, the computational methods based on broken-symmetry (BS) UB3LYP solutions have been developed to elucidate magnetic interactions in the active manganese catalyst for water oxidation by sunlight. The effective exchange interactions J for the CaMn(III)Mn(IV)₃O₅(H₂O)₃Y(Y = H₂O or OH^?) cluster (1) model of OEC of PSII have been calculated by the generalised approximate spin projection (GAP) method that eliminates the spin contamination errors of the BS UB3LYP solution. Full geometry optimisations followed by the zero-point energy (ZPE) correction have been performed for all the spin configurations of 1 to improve the J values that are compared with accumulated EPR in the S₂ state of Kok cycle and magnetic susceptibility results of Christou model complex Ca₂Mn(IV)₃O₄ (2). Using the calculated J values, exact diagonalisation of the spin Hamiltonian matrix has been carried out to obtain excitation energies and spin densities of the ground and lower excited states of 1. The calculated excitation energies are consistent with the available experimental results. The calculated spin densities (projection factors) are also compatible with those of the EPR results. The calculated spin densities have been used to calculate the isotropic hyperfine (A_iso) constants of ⁵⁵Mn ions revealed by the EPR experiments. Implications of the computational results are discussed in relation to the structural symmetry breaking (SSB) in the S₁, S₂ and S₃ states, spin crossover phenomenon induced by the near-infrared excitation and the right- and left-handed scenarios for the O–O bond formation for water oxidation.     

Magnetic properties of the cyclic spincluster Fe6:bicine

The magnetic properties of the cyclic compound [Fe₆(bicine)₆] LiClO₄ ^. 2MeOH are reported. The cluster Fe₆(bicine)₆ forms an antiferromagnetically coupled ring structure of Fe ^III ions. The magnetic susceptibility is measured between 2 and 300 K and yields the exchange coupling of J/k _B = - 27.5±0.5 K. The field dependence of the magnetic moment is studied at 3 and 6 K in magnetic fields up to 5 T. The zero-field splitting of the first excited spin states with S = 2 and 3 are determined by ESR at 94 GHz. The intra-molecular interactions of the Fe ^III ions are analyzed and the on-site anisotropy of the Fe ^III due to the ligand-configuration is determined to d /k _B = - 0.633±0.008K. Received 28 October 2002 / Received in final form 22 February 2003 Published online 20 June 2003 RID="a" ID="a"e-mail: bernd@piobelix.physik.uni-karlsruhe.de     

Magnetic interactions in Pr3+ : LiYF4 for quantum manipulation : search for an efficient three-level Λ system

The influence of an external magnetic field on the hyperfine structure of the ³ H₄(0) and ¹D₂(0) crystal field states of Pr³⁺ in LiYF₄ is studied in order to find an efficient three-level Λ system. Using an experimentally determined spin Hamiltonian, we show that three-level Λ systems can be obtained with equal strengths for the optically excited transitions under various magnetic field magnitudes and orientations. An analytical analysis based on two levels is proposed to find useful magnetic fields without extensive numerical calculations and to understand the general behaviour of the system. Pr³⁺ hyperfine structure has also been directly calculated using a complete Hamiltonian including free ion, crystal field and magnetic interactions. A good agreement with the spin Hamiltonian approach is found for the ground state whereas the excited state results poorly reproduce the experiment. This is attributed to the low accuracy of ¹D₂ crystal field wavefunctions. This suggests that transition strengths ratios could be calculated directly from the crystal field Hamiltonian with improved crystal field parameters.     

Influence of chirality on the electron spin resonance in molecular magnets [MnII(H L )(H2O)][MnIII(CN)6] · 2H2O with chiral ligands L

Chiral and racemic molecular ferrimagnets [Mn^II(HL)(H₂O)][Mn^III(CN)₆] · 2H₂O, where L = S-or R-1,2-diaminopropane for chiral samples (S-pn, R-pn) and L = rac-pn for racemic samples, are investigated by the electron spin resonance technique. It is revealed that the electron spin resonance spectra of the chiral and racemic samples differ from each other at temperatures below the Curie temperature T _C = 21 K. The maximum in the temperature dependence of the integrated magnetic susceptibility χ(T) calculated by the double integration of the line centered at a negative field of −250 Oe for the racemic samples is broadened as compared to the maxima in the corresponding dependences for the enantiomers of the chiral samples with “right” (R) and “left” (S) symmetry. The new compounds under investigation differ from the previously synthesized crystals by the strong spin-orbit interaction between Mn³⁺ ions, which leads to a dependence of their magnetic properties on the chirality of the structure. Original Russian Text ? R.B. Morgunov, F.B. Mushenok, M.V. Kirman, 2008, published in Fizika Tverdogo Tela, 2008, Vol. 50, No. 7, pp. 1252–1256.     

Mixed valence states in cobalt iron cyanide

Cobalt iron cyanide with both Co and Fe in mixed valence states were prepared and characterized. In this mixed valence system the cobalt atom is found both as high spin Co(2+) and low spin Co(III) while iron always appears in low spin state to form two solid solutions: Co(2+)Co(III) hexacyanoferrates (II,III), and Co(2+)Co(III) hexacyanoferrate (II). Such solid solutions have the following formula units: (Co²⁺)_x(Co^III)_1−xK[(Fe^II)_1−x(Fe^III)_x(CN)₆]·H₂O and (Co²⁺)_1.5x(Co^III)_1−xK[Fe^II(CN)₆]·yH₂O (0?x?1, 1?y?14). Compounds within these two series were characterized from Infrared, Mössbauer, X-ray diffraction and thermo-gravimetric data, and magnetic measurements at low temperature. A model for their crystal structure is proposed and the structure for a representative composition refined from XRD powder patterns using the Rietveld method. A simple and reproducible procedure to prepare these solid solutions is provided. Within hexacyanoferrates, such mixed valence states system in both metal centres shows unique features, which are discussed from the obtained data.     

Finite-temperature characterization and simulations of the molecular assemblies Mn 6 and Ni 12

Numerical transfer-matrix approach and exact diagonalization technique exploiting the point-group symmetry and the properties of the shift operator are worked out in the framework of quantum statistical mechanics for the isotropic Heisenberg spin Hamiltonian with the ring geometry. They are applied in large-scale simulations to the title high nuclearity cyclic clusters Mn₆ (i.e. [Mn(hfac)₂NITPh]₆) and Ni₁₂ (i.e. Ni₁₂(O₂CMe)₁₂(chp)₁₂(H₂O)₆(THF)₆) in order to model quantitatively their magnetic properties. For Ni₁₂ complex new experimental susceptibility data are also reported. New microscopic spin model parameters for both molecules are obtained from a fit of the theoretical susceptibility curves to the experimental results.     

Perfect Transfer of Entangled States on Spin Chain

Current researches have shown that perfect states transfer over arbitrary distances is possible for a simple unmodulated spin chain by some schemes. The transfer of a single qubit state has been investigated in detail by Christandl et al. [Phys. Rev. Lett. 92, 187902(2004)] through a modified Heisenberg XX model Hamiltonian H _G . The previous study of Christandl is restricted to the first-excitation states of H _G (i.e., which correspond to the second subspace of the Hilbert space of H _G ). In this work, we extend their study to the case of the high-excitation states, and find that the entangled states in such a form, | ψ 〉 = α | 00⋯ 0〉 + β | 11⋯ 1〉, can be perfectly transfered on the spin chain. PACS numbers 03.67.Hk, 03.67.Pp, 05.50.+q.     

Domain wall dynamics of the spin-$\frac{1}{2}$ Ising-like antiferromagnetic chain in presence of Dzyaloshinskii-Moriya interactions

We consider a one-dimensional Ising-like S = \frac12\frac{1}{2} Heisenberg antiferromagnetic Hamiltonian and study the dynamics of domain wall excitations in presence of both uniform and staggered Dzyaloshinskii-Moriya interactions. We obtain dispersion relations and dynamical spin correlation functions, S ^{x x} (q, ω) using the basis of domain wall pair states. It is shown that the line shapes of S ^{x x} (q, ω) are highly asymmetric over the whole Brillouin zone such that the spectral weights mainly concentrate in the low energy side. It is observed that presence of staggered Dzyaloshinskii-Moriya interaction explains the experimental results on the Ising-like antiferromagnetic compounds CsCoCl₃ and CsCoBr₃ very well.     

Phase transition in antiferromagnets with anisotropic exchange interactions and uniaxial anisotropy

Abstract

Following the Bogoliubov variational principle, the equilibrium and stability equations of the free energy for the two sublattice antiferromagnetic system with inter- and intrasublattice exchange interactions and with an external magnetic field are investigated. For the Ising spin system with uniaxial anisotropy, the phase diagrams have been calculated for various values of anisotropy constant d and the ratio of intra- to intersublattice interaction constants γ. It is shown that first-order, as well as second-order transitions, occur for γ > 0, whereas only a second-order transition occurs for γ ≦ 0, irrespective of the sign of d. Furthermore, similar calculations are extended for the anisotropic Heisenberg spin system and quite interesting phase diagrams have been obtained. Next, the effects of the anisotropic exchange interactions on the magnetic ordered states and the magnetizations of the singlet ground state system of spin one and with a uniaxial anisotropy term are investigated in the vicinity of the level crossing field H ? D/gμ _B . A field-induced ordered state without the transverse component of magnetization is shown to appear in a certain range of magnetic field as the spin dimensionality decreases. It has also turned out that the phase transition between this ordered state and the canted antiferromagnetic state ordinarily found for the isotropic singlet ground state system is of first order. Lastly, the stable spin configurations at a temperature of absolute zero for a two-sublattice uniaxial antiferromagnet under an external magnetic field of arbitrary direction are studied. In particular, the effects of a single ionic anisotropy D-term and anisotropy in the exchange interactions on the magnetic phases are investigated. The antiferromagnetic state has turned out to appear only for the external magnetic field along the easy axis of sublattice magnetization, and makes a first-order phase transition to the canted-spin state or the ferromagnetic state. For other field directions, no antiferromagnetic state appears and only a second-order phase transition between the canted-spin and the ferromagnetic states occurs. The critical field as a function of external field direction has been calculated for several D-values.     

Highly efficient spin polarizer based on individual heterometallic cubane single-molecule magnets

The spin-polarized transport across a single-molecule magnet [Mn₃Zn(hmp)₃O(N₃)₃(C₃H₅O₂)₃]·2CHCl₃ has been investigated using a density functional theory combined with Keldysh non-equilibrium Green’s function formalism. It is shown that this single-molecule magnet has perfect spin filter behaviour. By adsorbing Ni₃ cluster onto non-magnetic Au electrode, a large magnetoresistance exceeding 172% is found displaying molecular spin valve feature. Due to the tunneling via discrete quantum-mechanical states, the I–V curve has a stepwise character and negative differential resistance behaviour.     

Isotope effect in charge transport of LuB12

The galvanomagnetic properties of single-crystal samples with various isotopic boron compositions have been investigated for the first time for the normal state of superconductor LuB₁₂ (T c ≈ 0.44 K). Precision measurements of the resistivity, Hall coefficient, and magnetic susceptibility have been performed over a wide temperature range of 2–300 K in magnetic fields up to 80 kOe. A change of the charge transport regime in this nonmagnetic compound with metallic conduction is shown to occur near T* ≈ 50−70 K. As a result, a sharp peak with significantly different amplitudes for Lu¹⁰B₁₂ and Lu¹¹B₁₂ is recorded in the temperature dependences of the Hall coefficient R _H(T) near T*. A significant (about 10%) difference (in absolute value) of the Hall coefficients R _H for the Lu¹⁰B₁₂ and Lu¹¹B₁₂ compounds at helium and intermediate temperatures has been found and the patterns of behavior of the dependence R _H(H) for T < T* in an external magnetic field H ≤ 80 kOe for Lu¹⁰B₁₂ and Lu¹¹B₁₂ are shown to differ significantly. Analysis of the Curie-Weiss contribution to the magnetic susceptibility χ(T) leads to the conclusion about the formation of magnetic moments μ_eff ≈ (0.13−0.19)μ_B in each unit cell of the fcc structure of LuB₁₂ compounds with various isotopic compositions. The possibility of the realization of an electronic topological 2.5-order transition near T* and the influence of correlation effects in the 5d-band on the formation of a spin polarization near the rare-earth ions in LuB₁₂ is discussed.     

NaZn13型结构LaFe13－xAlxCy化合物的磁熵变与磁相变的研究

研究了NaZn₁₃型结构LaFe_13-xAl_xC_0.1(x=1.6，1.8)间隙化合物的磁制冷能力和磁相变.利用麦克斯韦关系式计算得到，高Al含量LaFe_13-xAl_x碳化物的最大磁熵变值|ΔS|_m低于低Al含量碳化物的最大磁熵变值.随Al含量的增加，化合物的磁熵变峰展宽，但由于磁熵变大幅降低，衡量磁制冷能力的q值随之降低.基于朗道相变原理，考虑到自旋涨落的影响，磁自由能可以展开到磁化强度的6次方项，材料的相变类型由磁化强度的4次方项系数a₃(T)的符号来进行判断.随着Al含量的增加，研究的碳化物相变由弱的一级相变转为二级相变. 关键词： 13-xAl_x碳化物')" href="#">LaFe_13-xAl_x碳化物 磁制冷能力 磁相变     

Reduced magnetic disorder at low temperature in Ca3Co2O6 via zinc substitution

ABSTRACT

The compound Ca₃Co₂O₆ undergoes a transition into a spin-density wave (SDW) state near 24?K. Below ～10?K, this unstable SDW state coexists with a nearly- degenerate commensurate antiferromagnetic state as well as short-range magnetic order. Clear signatures of this strong magnetic disorder have been observed in the response of entropy to changing magnetic field and temperature. We performed a calorimetry study of Ca₃Co₂O₆ and Ca₃Co_1.9Zn_0.1O₆ in order to compare their entropic responses at low temperature. Our results for Ca₃Co₂O₆ reveal that ΔS(T, H)?≡?S(T, H)?S(T, H?=?0) increases as either temperature or magnetic field increase. In contrast, ΔS data for Ca₃Co_1.9Zn_0.1O₆ were relatively unresponsive to changes in temperature or field, suggesting that Zn substitution may reduce the low-temperature magnetic disorder observed in Ca₃Co₂O₆. These results are discussed within the context of two cases (Ca₃Co₂O₆ under applied pressure and Ca_2.75R_0.25Co₂O₆ (R?=?Dy, Lu)) in which a single magnetic ground state is stabilised.     

EPR spectrum of gadolinium in hydrated praseodymium sulphate

The electron paramagnetic resonance of Gd³⁺ in single crystal of Pr₂(SO₄)₃.8H₂O is studied at room temperature. Two magnetic complexes exhibiting orthorhombic or lower symmetry are found and the results have been fitted to a suitable spin Hamiltonian. The exact solution of Hamiltonian matrix is carried out and 10 “best fit” parameters are obtained using iterative optimization technique. The zero field splittings of Gd³⁺: Pr₂(SO₄)₃.8H₂O have been computed. Few forbidden transitions are observed and explained using numerical solution of the Hamiltonian matrix.     

On bistability in molecular systems: Photomagnetic studies of inorganic complexes

Photo‐induced effects have been detected by magnetic measurements, Mössbauer spectroscopy and reflectivity. The LIESST effect has been achieved in the spin‐crossover system [Fe_xCo_1-x(btr)₂(NCS)₂]·H₂O. We investigated the purely photo‐induced magnetism of a Prussian Blue analogue Rb_0.52Co[Fe(CN)₆]_0.84, 2.31 H₂O, involving an optical electron transfer from Fe^II to Co^III. Inherent aspects of photomagnetic experiments are described: bulk and surface effects, magnetic and electronic metastabilities of the photo‐excited state.     

Static and dynamic effects in the EPR spectra of [A(H2O)6]BF6 systems

EPR studies of [Mg(H₂O)₆]BF₆ (B=Si, Ge) crystals are performed by using Mn²⁺ paramagnetic probes. The temperature dependence of the EPR spectra shows that the crystals undergo a ferroelastic phase transition to a monoclinic phase. In both systems the ferroelastic phase transition is preceded by intermediate states. The spin Hamiltonian parameters determined in the low and high temperature phases of the systems are useful to precise some aspects of the local atomic displacements involved in the intermediate states. The nature of this state is analyzed in the framework of different models as well.     

Mössbauer spectroscopic studies of [Fe(H2O)6]3+ in amorphous frozen solutions at weak applied magnetic fields

The ferric hexaquo complex, [Fe(H₂O)₆]³⁺, has been studied by Mössbauer spectroscopy of amorphous aqueous frozen solutions at weak applied magnetic fields. Spectra of well resolved paramagnetic hyperfine structure have been interpreted in terms of a spin Hamiltonian model for the crystal field interaction proposed in a previous work. Reasonable fits could be obtained only by the addition of a random magnetic field of a few Gauss which is attributed partly to the dipolar interaction with neighbouring iron ions, and partly to the ligand hyperfine interaction.     

Effect of chirality on domain wall dynamics in molecular ferrimagnet [Mn<Superscript>II</Superscript>(HL-pn)(H<Subscript>2</Subscript>O)][Mn<Superscript>III</Superscript>(CN)<Subscript>6</Subscript>]·2H<Subscript>2</Subscript>O

In this paper we distinguish the contributions of switching, slide, creep and Debye relaxation modes of the domain wall dynamics to the low-frequency magnetic properties of chiral and racemic [Mn^II(HL-pn)(H₂O)][Mn^III(CN)₆]·2H₂O molecular ferrimagnets. We demonstrate that crystal and spin chirality affects the characteristic transition temperatures between different modes. In chiral crystals, transitions to the creep and Debye relaxation modes were observed at T = 7 K and 5 K, whereas in racemic crystals the same transitions occurred at higher temperatures T = 13 K and 9 K, respectively. Difference of the Peierls relief in chiral and racemic crystals is a possible reason of the chirality effect on the domain walls dynamics.     

The structural transformation of monoclinic [(R)-C5H14N2][Cu(SO4)2(H2O)4]·2H2O into orthorhombic [(R)-C5H14N2]2[Cu(H2O)6](SO4)3: crystal structures and thermal behavior

Single crystals of [(R)-C₅H₁₄N₂][Cu(SO₄)₂(H₂O)₄]·2H₂O (1) were grown through the slow evaporation of a solution containing H₂SO₄, (R)-C₅H₁₂N₂ and CuSO₄·5H₂O. These crystals spontaneously transform to [(R)-C₅H₁₄N₂]₂[Cu(H₂O)₆](SO₄)₃ (2) over the course of four days at room temperature. The same single crystal on the same mounting was used for the determination of the structure of (1) and the unit cell determination of (2). A second single crystal of the transformed batch has served for the structural determination of (2). Compound 1 crystallizes in the noncentrosymmetric space group P2₁ (No. 4) and consists of trimeric [Cu(SO₄)₂(H₂O)₄]^2? anions, [(R)-C₅H₁₄N₂]²⁺ cations and occluded water molecules. Compound 2 crystallizes in P2₁2₁2 (No. 18) and contains [Cu(H₂O)₆]²⁺ cations, [SO₄]^2? anions and occluded water molecules. The thermal decompositions of compounds 1 and 2 were studied by thermogravimetric analyses and temperature-dependent X-ray diffraction.     

二硫酸-二元胺锰和二羟基-二元胺锰纳米片磁性的第一性原理研究

We perform first-principles simulations on a type of two-dimensional metal-organic nanosheet derived from the recently reported manganese bis-dithiolene Mn₃C₁₂S₁₂ [Nanoscale 5, 10404 (2013)] and manganese bis-diamine Mn₃C₁₂N₁₂H₁₂ [ChemPhysChem 16, 614 (2015)] mono-layers. By coordinating chalcogen (S or O) atoms and -NH- group to Mn atoms with trans- or cis-structures and preserving space inversion symmetry, four configurations of this type of nanosheet are obtained: trans-manganese dithiolene-diamine Mn₃(C₆S₃N₃H₃)₂, cis- manganese dithiolene-diamine Mn₃(C₆S₆)(C₆N₆H₆), trans-manganese dihydroxyl-diamine Mn₃(C₆O₃N₃H₃)₂, and cis-manganese dihydroxyl-diamine Mn₃(C₆O₆)(C₆N₆H₆). The ge- ometric con guration, electronic structure and magnetic properties of these metal-organic nanosheets are systematically explored by density functional theory calculations. The cal- culated results show that Mn₃(C₆S₃N₃H₃)₂, Mn₃(C₆O₃N₃H₃)₂ and Mn₃(C₆O₆)(C₆N₆H₆) monolayers exhibit half-metallicity and display strong ferromagnetism with Curie transition temperatures near and even beyond room temperature, and Mn₃(C₆S₆)(C₆N₆H₆) monolayer is a semiconductor with small energy gap and spin frustration ground state. The mechanisms for the above properties, especially in uences of diflerent groups (atoms) substitution and coordination style on the magnetism of the nanosheet, are also discussed. The predicted two-dimensional metal-organic nanosheets have great promise for the future spintronics ap-plications.