Probing photoinduced spin states in spin-crossover molecules with neutron scattering

We report a neutron scattering investigation of the spin crossover compound \rm [Fe(ptz)6](BF4)2 which undergoes an abrupt thermal spin-transition from high-spin (HS) S=2 to low-spin (LS) S=0 around 135 K. The HS magnetic state can be restored at low temperature under blue/green light irradiation. We have developed a specially designed optical setup for neutron scattering to address the magnetic properties of the light-induced HS state. By using neutron diffraction, we demonstrate that significant HS/LS ratios (of up to 60 \%) can be obtained with this experimental setup on a sample volume considered large (400 mg), while a complete recovery of the LS state is achieved using near infrared light. With inelastic neutron scattering (INS) we have observed, for the first time in a photo-induced phase, magnetic transitions arising from the metastable HS S=2 state split by crystal field and spin-orbit coupling. We interpret the INS data assuming a spin-only model with a zero-field splitting (ZFS) of the S=2 ground state. The obtained parameters are D \approx -1.28 \pm 0.03 meV and |E| \approx 0.08 \pm 0.03 meV. The present results show that in situ magnetic inelastic neutron scattering investigations on a broad range of photomagnetic materials are now possible

Magnetic relaxation phenomena and cluster glass properties of La{0.7-x}Y{x}Ca{0.3}MnO{3} manganites

The dynamic magnetic properties of the distorted perovskite system La{0.7-x}Y{x}Ca{0.3}MnO{3} (0 <= x <= 0.15) have been investigated by ac-susceptibility and dc magnetization measurements, with emphasis on relaxation and aging studies. They evidence for x >= 0.10 the appearance of a metallic cluster glass phase, that develops just below the ferromagnetic transition temperature. The clusters grow with decreasing temperature down to a temperature T(f0) at which they freeze due to severe intercluster frustration. The formation of these clusters is explained by the presence of yttrium induced local structural distortions that create localized spin disorder in a magnetic lattice where double-exchange ferromagnetism is dominant.Comment: Accepted for publication in Phys. Rev.

Magnetisation Studies of Geometrically Frustrated Antiferromagnets SrLn2O4, with Ln = Er, Dy and Ho

We present the results of susceptibility \chi(T) and magnetisation M(H) measurements performed on single crystal samples of the rare-earth oxides SrLn2O4 (Ln = Er, Dy and Ho). The measurements reveal the presence of magnetic ordering transition in SrHo2O4 at 0.62 K and confirm that SrEr2O4 orders magnetically at 0.73 K, while in SrDy2O4 such a transition is absent down to at least 0.5 K. The observed ordering temperatures are significantly lower than the Curie-Weiss temperatures, \theta_{CW}, obtained from the high-temperature linear fits to the 1/\chi(T) curves, which implies that these materials are subject to geometric frustration. Strong anisotropy found in the \chi(T) curves for a field applied along the different crystallographic directions is also evident in the M(H) curves measured both above and below the ordering temperatures. For all three compounds the magnetisation plateaux at approximately one third of the magnetisation saturation values can be seen for certain directions of applied field, which is indicative of field-induced stabilisation of a collinear {\it two-up one-down} structure.Comment: 6 pages, 6 figure

Phase Competition in Ln0.5a0.5mno3 Perovskites

Single crystals of the systems Pr0.5(Ca1-xSrx)0.5MnO3, (Pr1-yYy)0.5(Ca1-xSrx)0.5MnO3, and Sm0.5Sr0.5MnO3 were grown to provide a series of samples with fixed ratio Mn(III)/Mn(IV)=1 having geometric tolerance factors that span the transition from localized to itinerant electronic behavior of the MnO3 array. A unique ferromagnetic phase appears at the critical tolerance factor tc= 0.975 that separates charge ordering and localized-electron behavior for t<tc from itinerant or molecular-orbital behavior for t>tc. This ferromagnetic phase, which has to be distinguished from the ferromagnetic metallic phase stabilized at tolerance factors t>tc, separates two distinguishable Type-CE antiferromagnetic phases that are metamagnetic. Measurements of the transport properties under hydrostatic pressure were carried out on a compositions t a little below tc in order to compare the effects of chemical vs. hydrostatic pressure on the phases that compete with one another near t=tc.Comment: 10 pages. To be publised in Phys. Rev.

Orbital ordering in the manganites: resonant x-ray scattering predictions at the manganese LII and LIII edges

It is proposed that the observation of orbital ordering in manganite materials should be possible at the L II and L III edges of manganese using x-ray resonant scattering. If performed, dipole selection rules would make the measurements much more direct than the disputed observations at the manganese K edge. They would yield specific information about the type and mechanism of the ordering not available at the K edge, as well as permitting the effects of orbital ordering and Jahn-Teller ordering to be detected and distinguished from one another. Predictions are presented based on atomic multiplet calculations, indicating distinctive dependence on energy, as well as on polarization and on the azimuthal angle around the scattering vector

Hole-doping dependence of percolative phase separation in Pr_(0.5-delta)Ca_(0.2+delta)Sr_(0.3)MnO_(3) around half doping

We address the problem of the percolative phase separation in polycrystalline samples of Pr$_{0.5-\delta}$Ca$_{0.2+\delta}$Sr$_{0.3}$MnO$_3$ for $-0.04\leq \delta \leq 0.04$ (hole doping $n$ between 0.46 and 0.54). We perform measurements of X-ray diffraction, dc magnetization, ESR, and electrical resistivity. These samples show at $T_C$ a paramagnetic (PM) to ferromagnetic (FM) transition, however, we found that for $n>0.50$ there is a coexistence of both of these phases below $T_C$. On lowering $T$ below the charge-ordering (CO) temperature $T_{CO}$ all the samples exhibit a coexistence between the FM metallic and CO (antiferromagnetic) phases. In the whole $T$ range the FM phase fraction ($X$) decreases with increasing $n$. Furthermore, we show that only for $n\leq 0.50$ the metallic fraction is above the critical percolation threshold $X_C\simeq 15.5$. As a consequence, these samples show very different magnetoresistance properties. In addition, for $n\leq 0.50$ we observe a percolative metal-insulator transition at $T_{MI}$, and for $T_{MI}<T<T_{CO}$ the insulating-like behavior generated by the enlargement of $X$ with increasing $T$ is well described by the percolation law $\rho ^{-1}=\sigma \sim (X-X_C)^t$, where $t$ is a critical exponent. On the basis of the values obtained for this exponent we discuss different possible percolation mechanisms, and suggest that a more deep understanding of geometric and dimensionality effects is needed in phase separated manganites. We present a complete $T$ vs $n$ phase diagram showing the magnetic and electric properties of the studied compound around half doping.Comment: 9 text pages + 12 figures, submitted to Phys. Rev.

Suppression of charge-ordering and appearance of magnetoresistance in a spin-cluster glass manganite La0.3Ca0.7Mn0.8Cr0.2O3

The magnetic properties of electron-doped manganite La0.3Ca0.7MnO3 and La0.3Ca0.7Mn0.8Cr0.2O3 polycrystalline samples prepared by sol-gel technique have been investigated between 5 and 300 K in magnetic fields ranging from 0 to 5 T. The transition at 260 K, attributed to charge ordering in La0.3Ca0.7MnO3, is completely suppressed in the Cr-substituted sample while the onset of a magnetic remanence followed by the appearance of a magnetic irreversibility at lower temperatures is observed in both samples. These features indicate that ferromagnetic clusters coexist with either an antiferromagnetic phase for La0.3Ca0.7MnO3 or a spin-cluster glass phase for La0.3Ca0.7Mn0.8Cr0.2O3 at the lowest temperatures. The exponential temperature dependence of the resistivity for the Cr-substituted sample is consistent with the small polaron hopping model for 120 K < T < 300 K, while the data are better described by Mott's hopping mechanism for T < 120 K. Whereas the parent compound La0.3Ca0.7MnO3 is known to show no magnetoresistance, a large negative magnetoresistance is observed in the La0.3Ca0.7Mn0.8Cr0.2O3 sample below 120 K. The appearance of the CMR is attributed to spin dependent hopping between spin clusters and/or between ferromagnetic domains

Ising Universality in Three Dimensions: A Monte Carlo Study

We investigate three Ising models on the simple cubic lattice by means of Monte Carlo methods and finite-size scaling. These models are the spin-1/2 Ising model with nearest-neighbor interactions, a spin-1/2 model with nearest-neighbor and third-neighbor interactions, and a spin-1 model with nearest-neighbor interactions. The results are in accurate agreement with the hypothesis of universality. Analysis of the finite-size scaling behavior reveals corrections beyond those caused by the leading irrelevant scaling field. We find that the correction-to-scaling amplitudes are strongly dependent on the introduction of further-neighbor interactions or a third spin state. In a spin-1 Ising model, these corrections appear to be very small. This is very helpful for the determination of the universal constants of the Ising model. The renormalization exponents of the Ising model are determined as y_t = 1.587 (2), y_h = 2.4815 (15) and y_i = -0.82 (6). The universal ratio Q = ^2/ is equal to 0.6233 (4) for periodic systems with cubic symmetry. The critical point of the nearest-neighbor spin-1/2 model is K_c=0.2216546 (10).Comment: 25 pages, uuencoded compressed PostScript file (to appear in Journal of Physics A

Improved high-temperature expansion and critical equation of state of three-dimensional Ising-like systems

High-temperature series are computed for a generalized $3d$ Ising model with arbitrary potential. Two specific ``improved'' potentials (suppressing leading scaling corrections) are selected by Monte Carlo computation. Critical exponents are extracted from high-temperature series specialized to improved potentials, achieving high accuracy; our best estimates are: $\gamma=1.2371(4)$, $\nu=0.63002(23)$, $\alpha=0.1099(7)$, $\eta=0.0364(4)$, $\beta=0.32648(18)$. By the same technique, the coefficients of the small-field expansion for the effective potential (Helmholtz free energy) are computed. These results are applied to the construction of parametric representations of the critical equation of state. A systematic approximation scheme, based on a global stationarity condition, is introduced (the lowest-order approximation reproduces the linear parametric model). This scheme is used for an accurate determination of universal ratios of amplitudes. A comparison with other theoretical and experimental determinations of universal quantities is presented.Comment: 65 pages, 1 figure, revtex. New Monte Carlo data by Hasenbusch enabled us to improve the determination of the critical exponents and of the equation of state. The discussion of several topics was improved and the bibliography was update