Phase transitions anion ordering

General overviews of STM studies of metal electrodes have been provided [10, 23-25] in addition, an extensive review that focused on ordered anion monolayers on metal electrode surfaces has been published [26]. Charge-induced surface phase transitions on ordered Au(lll) caused by increasing iodide adsorption from an aqueous electrolyte solutions have been observed [27]. The formation of copper sulflde nanostripe patterns on a Au(lll) electrode surface formed by exposure of a single copper monolayer on this electrode and exposed to bisulfide ions in the electrolyte solution has been studied with in situ STM [28]. Correlations between... 

Also known for some time is a phase transition at low temperature (111K), observed in studies with various methods (NQR, elasticity measurement by ultrasound, Raman spectrometry) 112 temperature-dependent neutron diffraction showed the phase transition to be caused by an antiphase rotation of adjacent anions around the threefold axis ([111] in the cubic cell) and to lower the symmetry from cubic to rhombohedral (Ric). As shown by inelastic neutron scattering, this phase transition is driven by a low-frequency rotatory soft mode (0.288 THz 9.61 cm / 298 K) 113 a more recent NQR study revealed a small hysteresis and hence first-order character of this transition.114 This rhombohedral structure is adopted by Rb2Hg(CN)4 already at room temperature (rav(Hg—C) 218.6, rav(C—N) 114.0 pm for two independent cyano groups), and the analogous phase transition to the cubic structure occurs at 398 K.115... 

In the paramagnetic regime, the evolution of the EPR line width and g value show the presence of two transitions, observed at 142 and 61 K in the Mo salt, and at 222 and 46 K in the W salt. Based on detailed X-ray diffraction experiments performed on the Mo salt, the high temperature transition has been attributed to a structural second-order phase transition to a triclinic unit cell with apparition of a superstructure with a modulation vector q = (0,1/2, 1/2). Because of a twinning of the crystals at this transition, it has not been possible to determine the microscopic features of the transition, which is probably associated to an ordering of the anions, which are disordered at room temperature, an original feature for such centrosymmetric anions. This superstructure remains present down to the Neel... 

The phase transition consists of a cooperative mechanism with charge-ordering, anion order-disorder, Peierls-like lattice distortion, which induces a doubled lattice periodicity giving rise to 2 p nesting, and molecular deformation (Fig. 11c). The high temperature metallic phase is composed of flat EDO molecules with +0.5 charge, while the low temperature insulating phase is composed of both flat monocations... 

Innocenti et al. have studied the kinetics [101] of two-dimensional phase transitions of sulfide and halide ions, as well as electrosorption valency [102] of these ions adsorbed on Ag(lll). The electrode potential was stepped up from the value negative enough to exclude anionic adsorption to the potential range providing stability of either the first or the second, more compressed, ordered overlayer of the anions. The kinetic behavior was interpreted in terms of a model that accounts for diffusion-controlled random adsorption of the anions, followed by the progressive polynucleation and growth. 

Phase transitions. Low-dimensional conductors undergo several types of specific structural phase transitions, such as the Peierls distortion (electron-phonon coupling), the spin-Peierls distortion (spin-phonon coupling), anion-ordering transitions, and so on. These first have to be detected and then measured and understood. However, the foregoing distortions may be very small and difficult to observe, and up to now, only a few lattice distortions have been fully measured and described. 

ESR measurements have been performed on three (ET) Re04 phases (97)y but x(T) is not known on an absolute scale. The results are shown in Fig. 22. The 2 1 salt has features similar to (TMTSF)2Re04 it has a constant susceptibility in the metallic regime and an abrupt transition to a very low value below Tm. The 3 2 salt has a %(T) similar to what one expects from a Peierls transition without influence of anion ordering, i.e., somewhat similar to TTF-TCNQ if scaled to the present Tw. Finally, the 2 1 salt has a rather featureless susceptibility with a... 

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