Spin-phase transitions

Geometric Spin Frustration and Spin-Phase Transitions... 

A pronounced hysteresis of ATC = 9.5 K has been observed (Tc = 181.86 K for rising and Tc = 172.33 K for falling temperature). The authors attempted to describe the results with the thermodynamic model for spin transitions of Slichter and Drickamer 91 Different diffraction patterns were recorded above and below Tc, where only one spin isomer was present (see Fig. 39). This provides evidence that a crystallographic phase change accompanies the abrupt spin phase transition in this compound. The temperature dependence of the peak profiles was found to follow that of the HS fraction as derived from the Mossbauer spectra, which shows that the crystallographic phase change is directly associated with the interconversion of the two spin phases. The Debye-Waller factors were evaluated for the two spin phases they showed at Tc a discontinuity of Af 35% on going from the HS to the LS phase. The shape of the transition curve near Tc and Tc itself, were somewhat different in three independently prepared samples. 

Fig. 5 The unit cell parameter of a powdered sample of [FeL2](Bp4)2 [L=2,6-di(pyrazol-l-yl)pyridine] determined from laboratory powder diffraction data. Structural changes at the low- to high-spin phase transition are readily visible. View this art in color at www.dekker.com.)...

K. Binder, P. C. Hoehenberg. Phase transitions and static spin correlations in Ising models with free surfaces. Phys Rev B 6 3461-3487, 1972. 

It should be realized that unlike the study of equilibrium thermodynamics for which a model is often mapped onto Ising system, elementary mechanism of atomic motion plays a deterministic role in the kinetic study. In an actual alloy system, diffusion of an atomic species is mainly driven by vacancy mechanism. The incorporation of the vacancy mechanism into PPM formalism, however, is not readily achieved, since the abundant freedom of microscopic path of atomic movement demands intractable number of variational parameters. The present study is, therefore, limited to a simple spin kinetics, known as Glauber dynamics [14] for which flipping events at fixed lattice points drive the phase transition. Hence, the present study for a spin system is regarded as a precursor to an alloy kinetics. The limitation of the model is critically examined and pointed out in the subsequent sections. 

This tells us immediately that, just as for Ising spins, we have a spontaneous magnetization and that there is an effective phase transition for T = 1 stored patterns will only be stable for temperatures T < 1. 

Methane-to-methanol conversion by gas-phase transition metal oxide cations has been extensively studied by experiment and theory see reviews by Schroder, Schwarz, and co-workers [18, 23, 134, 135] and by Metz [25, 136]. We have used photofragment spectroscopy to study the electronic spectroscopy of FeO" " [47, 137], NiO [25], and PtO [68], as well as the electronic and vibrational spectroscopy of intermediates of the FeO - - CH4 reaction. [45, 136] We have also used photoionization of FeO to characterize low lying, low spin electronic states of FeO [39]. Our results on the iron-containing molecules are presented in this section. 

Ammonium alums undergo phase transitions at Tc 80 K. The phase transitions result in critical lattice fluctuations which are very slow close to Tc. The contribution to the relaxation frequency, shown by the dotted line in Fig. 6.7, was calculated using a model for direct spin-lattice relaxation processes due to interaction between the low-energy critical phonon modes and electronic spins. 

I2H2O as a function of the reciprocal temperature. The points are data obtained from fits of the Mdssbauer spectra (Fig. 6.6). The broken curve is a fit to the Einstein model for a Raman process. The dotted curve corresponds to a contribution from a direct process due to interactions between the electronic spins and low-energy phonons associated with critical fluctuations near the phase transition temperature. (Reprinted with permission from [32] copyright 1979 by the Institute of Physics)... 

Phase transitions Spin and magnetic transitions Dynamic solid-state phenomena Solid-state reactions (e.g., thermolysis, radiolysis)... 

A series of NFS spectra of the spin-crossover complex [Fe(tpa)(NCS)2] were recorded over a wide temperature range [45]. A selection of spectra around the spin-crossover transition temperature is shown in Fig. 9.13. At 133 K, the regular quantum-beat structure reflects the quadrupole splitting from the pure high-spin (HS) phase, and the envelope of the spectrum represents the dynamical beating with a minimum around 200 ns. Below the transition, at 83 K, the QBs appear with lower frequency because of smaller AEq of the low-spin (LS) phase. Here the minima of... 

MnAs exhibits this behavior. It has the NiAs structure at temperatures exceeding 125 °C. When cooled, a second-order phase transition takes place at 125 °C, resulting in the MnP type (cf. Fig. 18.4, p. 218). This is a normal behavior, as shown by many other substances. Unusual, however, is the reappearance of the higher symmetrical NiAs structure at lower temperatures after a second phase transition has taken place at 45 °C. This second transformation is of first order, with a discontinuous volume change AV and with enthalpy of transformation AH. In addition, a reorientation of the electronic spins occurs from a low-spin to a high-spin state. The high-spin structure (< 45°C) is ferromagnetic,... 

Recently, due to increased interest in membrane raft domains, extensive attention has been paid to the cholesterol-dependent liquid-ordered phase in the membrane (Subczynski and Kusumi 2003). The pulse EPR spin-labeling DOT method detected two coexisting phases in the DMPC/cholesterol membranes the liquid-ordered and the liquid-disordered domains above the phase-transition temperature (Subczynski et al. 2007b). However, using the same method for DMPC/lutein (zeaxanthin) membranes, only the liquid-ordered-like phase was detected above the phase-transition temperature (Widomska, Wisniewska, and Subczynski, unpublished data). No significant differences were found in the effects of lutein and zeaxanthin on the lateral organization of lipid bilayer membranes. We can conclude that lutein and zeaxanthin—macular xanthophylls that parallel cholesterol in its function as a regulator of both membrane fluidity and hydrophobicity—cannot parallel the ability of cholesterol to induce liquid-ordered-disordered phase separation. 

Wisniewska, A., Y. Nishimoto, J. S. Hyde, A. Kusumi, and W. K. Subczynski. 1996. Depth dependence of the perturbing effect of placing a bulky group (oxazoline ring spin labels) in the membrane on the membrane phase transition. Biochim. Biophys. Acta 1278 68-72. 

Morrisett, et al.17 studied phase transitions in E. coli membranes using three different spin labels, including 5-doxyl stearate (5-DS) (7). 

They observed abrupt changes in the slope of Arrhenius plots for reactions catalyzed by NADH oxidase and p-lactate oxidase that correlate well with phase transitions detected by the ESR spectra of the nitroxide spin labels bound covalently to the enzymes (Table 5.4). 

In order to obtain kinetic parameters for the electron transfer of [11] /K +, the dephasing time tm of the electron-spin echo near the phase-transition temperature Tt was measured. These experiments gave a correlation time tc of 100 ns for the electron transfer at Tg = 170 K. From the assumption of an exponential decrease of c in solution, a value of 100 ps was estimated for tc at room temperature (Rautter, 1989 Rautter et al., 1992). 

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