Ferroelectrics hydrogen bonding

Keywords Ferroelectrics Hydrogen-bonded systems NMR techniques ... 

The entropy value of gaseous HCl is a sum of contributions from the various transitions summarized in Table 4. Independent calculations based on the spectroscopic data of H Cl and H Cl separately, show the entropy of HCl at 298 K to be 186.686 and 187.372 J/(mol K) (44.619 and 44.783 cal/(mol K), respectively. The low temperature (rhombic) phase is ferroelectric (6). SoHd hydrogen chloride consists of hydrogen-bonded molecular crystals consisting of zigzag chains having an angle of 93.5° (6). Proton nmr studies at low temperatures have also shown the existence of a dimer (HC1)2 (7). 

The crystal structure of many compounds is dominated by the effect of H bonds, and numerous examples will emerge in ensuing chapters. Ice (p. 624) is perhaps the classic example, but the layer lattice structure of B(OH)3 (p. 203) and the striking difference between the a- and 6-forms of oxalic and other dicarboxylic acids is notable (Fig. 3.9). The more subtle distortions that lead to ferroelectric phenomena in KH2PO4 and other crystals have already been noted (p. 57). Hydrogen bonds between fluorine atoms result in the formation of infinite zigzag chains in crystalline hydrogen fluoride... 

Stimulated by these observations, Odelius et al. [73] performed molecular dynamic (MD) simulations of water adsorption at the surface of muscovite mica. They found that at monolayer coverage, water forms a fully connected two-dimensional hydrogen-bonded network in epitaxy with the mica lattice, which is stable at room temperature. A model of the calculated structure is shown in Figure 26. The icelike monolayer (actually a warped molecular bilayer) corresponds to what we have called phase-I. The model is in line with the observed hexagonal shape of the boundaries between phase-I and phase-II. Another result of the MD simulations is that no free OH bonds stick out of the surface and that on average the dipole moment of the water molecules points downward toward the surface, giving a ferroelectric character to the water bilayer. 

Burrows AD (2004) Crystal Engineering Using Multiple Hydrogen Bonds 108 55-96 Bussmann-Holder A, Dalai NS (2007) Order/Disorder Versus or with Displacive Dynamics in Ferroelectric Systems. 124 1-21... 

Dalai NS, Gunaydin-Sen O, Bussmann-Holder A (2007) Experimental Evidence for the Coexistence of Order/Disorder and Displacive Behavior of Hydrogen-Bonded Ferroelectrics and Antiferroelectrics. 124 23-50 Dalai NS, see Bussmann-Holder A (2007) 124 1-21 Daul CA, see Atanasov M (2003) 106 97-125... 

A less well-documented effect is that of the phase-transition temperature of certain crystals which are very sensitive to deuteration. Some crystals of ferroelectric and antiferroelectric materials, and in particular dihydrogen phosphates and hydrogen selenites, which are extensively hydrogen bonded, display this effect (Blinc and Zeks, 1974). For some crystals, such as caesium... 

In this chapter we will mainly concentrate on hydrogen-bonded ferroelectrics, which were the first class of ferroelectrics where the coexistence of the different dynamics was postulated and observed [26,27]. In Chap. 2 of this volume (by Dalai et al. [51]) new experimental techniques and their advantages over conventional ones will be described together with their applications to hydrogen-bonded systems. The theoretical concept of bihnear... 

Theoretical Modelling of the Phase Transition Mechanism of Hydrogen-Bonded Ferroelectrics... 

In order to understand these extreme changes in physical and chemical properties of hydrogen-bonded systems, first attempts to model their dynamics were related to rather simple structures, as exhibited by the KDP family or squaric acid and its analogues. The isotope effects on their ferro- or anti-ferroelectric transition temperatures are listed in Table 1 together with the corresponding isotope exponent. 

Table 1 Isotope effects and exponent a various hydrogen-bonded systems on the ferroelectric transition temperatiu es for...

Abstract This chapter describes the experimentai compiement of theoretical models of the microscopic mechanism of ferroelectric transitions. We use the hydrogen-bonded compounds as examples, and attempt to show that the new experimental data obtained via recently developed high resolution nuclear magnetic resonance techniques for solids clearly support the hypothesis that the transition mechanism must involve lattice polarizability (i.e. a displacive component), in addition to the order/disorder behaviour of the lattices. 

Keywords Hydrogen-bonded ferroelectrics Order/disorder-displacive effects ... 

The basic crystal structure consists of P04 (or As04 ) tetrahedra alternating with the K" " (or NH4 ) ions along the c-axis. The P04 units are connected by 0-H...0 hydrogen bonds in the ab plane, forming a three-dimensional hydrogen-bonded lattice [2]. In the ferroelectric phases, the H atoms are localized such that the two close protons are both on the top of the oxygen ions of the XO4 units, as depicted in Fig. 4b. In the antiferroelectric... 

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