Phase diagram with an enhanced spin-glass region of the mixed Ising–XY magnet LiHo{x}Er{1-x}F{4}

We present the experimental phase diagram of LiHoxEr1-xF4, a dilution series of dipolar-coupled model magnets. The phase diagram was determined using a combination of ac susceptibility and neutron scattering. Three unique phases in addition to the Ising ferromagnet LiHoF4 and the XY antiferromagnet LiErF4 have been identified. Below x = 0.86, an embedded spin-glass phase is observed, where a spin glass exists within the ferromagnetic structure. Below x = 0.57, an Ising spin glass is observed consisting of frozen needlelike clusters. For x ∼ 0.3–0.1, an antiferromagnetically coupled spin glass occurs. A reduction of TC(x) for the ferromagnet is observed which disobeys the mean-field predictions that worked for LiHoxY1-xF4.

Crystalline, Mixed-Valence Manganese Analogue of Prussian Blue: Magnetic, Spectroscopic, X-ray and Neutron Diffraction Studies

The compound of stoichiometry Mn(II)3[Mn(III)(CN)6]2·zH2O (z = 12−16) (1) forms air-stable, transparent red crystals. Low-temperature single crystal optical spectroscopy and single crystal X-ray diffraction provide compelling evidence for N-bonded high-spin manganese(II), and C-bonded low-spin manganese(III) ions arranged in a disordered, face-centered cubic lattice analogous to that of Prussian Blue. X-ray and neutron diffraction show structured diffuse scattering indicative of partially correlated (rather than random) substitutions of [Mn(III)(CN)6] ions by (H2O)6 clusters. Magnetic susceptibility measurements and elastic neutron scattering experiments indicate a ferrimagnetic structure below the critical temperature Tc = 35.5 K.

Determination of the crystal and magnetic structure of the DyCrO4-scheelite polymorph by neutron diffraction

Neutron diffraction data of DyCrO4 oxide, prepared at 4 GPa and 833 K from the ambient pressure zircon-type, reveal that crystallize with the scheelite-type structure, space group I41/a. Accompanying this structural phase transition induced by pressure the magnetic properties change dramatically from ferromagnetism in the case of zircon to antiferromagnetism for the scheelite polymorph with a T N= 19 K. The analysis of the neutron diffraction data obtained at 1.2 K has been used to determine the magnetic structure of this DyCrO4-scheelite oxide which can be described with a k = [0, 0, 0] as propagation vector, where the Dy and Cr moments are lying in the ab-plane of the scheelite structure. The ordered magnetic moments are 10 µB and 1 µB for Dy+3 and Cr+5 respectively

Photochemically induced nuclear spin polarization in reaction centers of photosystem II observed by 13C-solid-state NMR reveals a strongly asymmetric electronic structure of the P680.+ primary donor chlorophyll

We report 13C magic angle spinning NMR observation of photochemically induced dynamic nuclear spin polarization (photo- CIDNP) in the reaction center (RC) of photosystem II (PS2). The light-enhanced NMR signals of the natural abundance 13C provide information on the electronic structure of the primary electron donor P680 (chlorophyll a molecules absorbing around 680 nm) and on the pz spin density pattern in its oxidized form, P680⨥. Most centerband signals can be attributed to a single chlorophyll a (Chl a) cofactor that has little interaction with other pigments. The chemical shift anisotropy of the most intense signals is characteristic for aromatic carbon atoms. The data reveal a pronounced asymmetry of the electronic spin density distribution within the P680⨥. PS2 shows only a single broad and intense emissive signal, which is assigned to both the C-10 and C-15 methine carbon atoms. The spin density appears shifted toward ring III. This shift is remarkable, because, for monomeric Chl a radical cations in solution, the region of highest spin density is around ring II. It leads to a first hypothesis as to how the planet can provide itself with the chemical potential to split water and generate an oxygen atmosphere using the Chl a macroaromatic cycle. A local electrostatic field close to ring III can polarize the electronic charge and associated spin density and increase the redox potential of P680 by stabilizing the highest occupied molecular orbital, without a major change of color. This field could be produced, e.g., by protonation of the keto group of ring V. Finally, the radical cation electronic structure in PS2 is different from that in the bacterial RC, which shows at least four emissive centerbands, indicating a symmetric spin density distribution over the entire bacteriochlorophyll macrocycle.

Spin alignment of extra electrons in K-phenanthrene clusters taken from the crystalline tripotassium-intercalated phenanthrene structure

The appearance of ferromagnetic correlations among π electrons of phenanthrene (C14H10) molecules in the herringbone structure is proven for K doped clusters both by ab initio quantum-chemistry calculations and by the direct solution of the many-body Pariser-Parr-Pople Hamiltonian. Magnetic ground states are predicted for one or three additional electrons per phenanthrene molecule. These results are a consequence of the small overlap between the lowest unoccupied molecular orbitals (and lowest unoccupied molecular orbitals + 1) of neutral neighboring phenanthrene molecules, which makes the gain in energy by delocalization similar to the corresponding increase due to the Coulomb interaction.

Spin dependence of slow neutron scattering by deuterons /

Work performed at the Argonne National Laboratory.

Neutron-mapping polymer flow: Scattering, flow visualization, and molecular theory

Flows of complex fluids need to be understood at both macroscopic and molecular scales, because it is the macroscopic response that controls the fluid behavior, but the molecular scale that ultimately gives rise to rheological and solid-state properties. Here the flow field of an entangled polymer melt through an extended contraction, typical of many polymer processes, is imaged optically and by small-angle neutron scattering. The dual-probe technique samples both the macroscopic stress field in the flow and the microscopic configuration of the polymer molecules at selected points. The results are compared with a recent tube model molecular theory of entangled melt flow that is able to calculate both the stress and the single-chain structure factor from first principles. The combined action of the three fundamental entangled processes of reptation, contour length fluctuation, and convective constraint release is essential to account quantitatively for the rich rheological behavior. The multiscale approach unearths a new feature: Orientation at the length scale of the entire chain decays considerably more slowly than at the smaller entanglement length.

Structure and physical properties of [µ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘')iron(II)] Bis(hexafluorophosphate), a new Fe(II) spin-crossover compound with a three-dimensional threefold interlocked crystal lattice

[μ-Tris(1,4-bis(tetrazol-1-yl)butane-N4,N4‘)iron(II)] bis(hexafluorophosphate), [Fe(btzb)3](PF6)2, crystallizes in a three-dimensional 3-fold interlocked structure featuring a sharp two-step spin-crossover behavior. The spin conversion takes place between 164 and 182 K showing a discontinuity at about T1/2 = 174 K and a hysteresis of about 4 K between T1/2 and the low-spin state. The spin transition has been independently followed by magnetic susceptibility measurements, 57Fe-Mössbauer spectroscopy, and variable temperature far and midrange FTIR spectroscopy. The title compound crystallizes in the trigonal space group P30¯(No. 147) with a unit cell content of one formula unit plus a small amount of disordered solvent. The lattice parameters were determined by X-ray diffraction at several temperatures between 100 and 300 K. Complete crystal structures were resolved for 9 of these temperatures between 100 (only low spin, LS) and 300 K (only high spin, HS), Z = 1 [Fe(btzb)3](PF  6)2:  300 K (HS), a = 11.258(6) Å, c = 8.948(6) Å, V = 982.2(10) Å3; 100 K (LS), a = 10.989(3) Å, c = 8.702(2) Å, V = 910.1(4) Å3. The molecular structure consists of octahedral coordinated iron(II) centers bridged by six N4,N4‘ coordinating bis(tetrazole) ligands to form three 3-dimensional networks. Each of these three networks is symmetry related and interpenetrates each other within a unit cell to form the interlocked structure. The Fe−N bond lengths change between 1.993(1) Å at 100 K in the LS state and 2.193(2) Å at 300 K in the HS state. The nearest Fe separation is along the c-axis and identical with the lattice parameter c.

The structure of the rare-earth phosphate glass(Sm2O3)0.205(P2O5)0.795 studied by anomalous dispersion neutron diffraction

The role of the Sm3+ ions in the structure of vitreous Sm2O3•4P2O5 has been investigated using the neutron diffraction anomalous dispersion technique, which employs the wavelength dependence of the real and imaginary parts of the neutron scattering length close to an absorption resonance. The data described here represent the first successful complete neutron anomalous dispersion study on an amorphous material. This experimental methodology permits one to determine exclusively the closest Sm• •• Sm separation. Knowledge of the R•••R (R = rare-earth) pairwise correlation is key to understanding the optical and magnetic properties of rare-earth phosphate glasses. The anomalous difference correlation function, ΔT''(r), shows a dominant feature pertaining to a Sm•••Sm separation, centred at 4.8 Å. The substantial width and marked asymmetry of this peak indicates that the minimum approach of Sm3+ ions could be as close as 4 Å. Information on other pairwise correlations is also revealed via analysis of T (r) and ΔT (r) correlation functions: Sm3+ ions display an average co-ordination number, n Sm(O), of 7, with a mean Sm–O bond length of 2.375(5) Å whilst the PO4 tetrahedra have a mean P–O bond length of 1.538(2) Å. Second- and third-neighbour correlations are also identified. These results corroborate previous findings. Such consistency lends support to the application of the anomalous dispersion technique to determine separations.