Longitudinal and Transverse Electrocaloric Effects in Glycinium Phosphite Ferroelectric

A modified proton ordering model of glycinium phosphite ferroelectric, which involves the piezoelectric coupling of the proton and lattice subsystems, is used for the investigation of the electrocaloric effect. The model also accounts for the dependence of the effective dipole moment on a hydrogen bond on an order parameter, as well as a splitting of parameters of the interaction between pseudospins in the presence of shear stresses. In the two-particle cluster approximation, the influence of longitudinal and transverse electric fields on components of the polarization vector and the dielectric permittivity tensor, as well as on thermal characteristics of the crystal, is calculated. Longitudinal and transverse electrocaloric effects are studied. The calculated electrocaloric temperature change is quite small, about 1K; however, it can change its sign under the influence of a transverse field.

Micro- and nano-size hydrogarnet clusters and proton ordering in calcium silicate garnet: Part I. The quest to understand the nature of “water” in garnet continues

The calcium-silicate garnets, grossular (Ca3Al2Si3O12), andradite (Ca3Fe23+Si3O12), and their solid solutions [Ca3(Alx,Fe1−x3+)2Si3O12], can incorporate various amounts of structural OH–. This has important mineralogical, petrological, rheological, and geochemical consequences and extensive experimental investigations have focused on the nature of “water” in these phases. However, it was not fully understood how OH- was incorporated and this has seriously hampered the interpretation of different research results. IR single-crystal spectra of several nominally anhydrous calcium silicate garnets, both “end-member” and solid-solution compositions, were recorded at room temperature and 80 K between 3000 and 4000 cm–1. Five synthetic hydrogarnets in the system Ca3Al2(SiO4)3-Ca3Al2(H4O4)3-Ca3Fe23+(SiO4)3-Ca3Fe23+(H4O4)3 were also measured via IR ATR powder methods. The various spectra are rich in complexity and show several OH- stretching modes at wavenumbers between 3500 and 3700 cm–1. The data, together with published results, were analyzed and modes assigned by introducing atomic-vibrational and crystal-chemical models to explain the energy of the OH- dipole and the structural incorporation mechanism of OH-, respectively. It is argued that OH- is located in various local microscopic- and nano-size Ca3Al2H12O12- and Ca3Fe23+H12O12-like clusters. The basic substitution mechanism is the hydrogarnet one, where (H4O4)4– ↔ (SiO4)4–, and various local configurations containing different numbers of (H4O4)4– groups define the cluster type. Some spectra also possibly indicate the presence of tiny hydrous inclusion phases, as revealed by OH- modes above about 3670 cm–1. They were not recognized in earlier studies. Published proposals invoking different hypothetical “defects” and coupled-substitution mechanisms involving H+ are not needed to interpret the IR spectra, at least for OH- modes above about 3560 cm–1. Significant mineralogical, petrological, and geochemical consequences result from the analysis and are discussed in the accompanying Part II (this issue) of the investigation.

Structural manifestation of partial proton ordering and defect mobility in ice Ih

High precision lattice-parameter measurements provide a potential roadmap to producing partially-ordered states of water ice.

Replica exchange MD simulations of two-dimensional water in graphene nanocapillaries: rhombic versus square structures, proton ordering, and phase transitions

Minimum energy structures of quasi-two dimensional ice confined between graphene sheets.

Proton ordering dynamics of H2O ice

Proton ordering in ice Ih and nucleation of ice XI domains are observed for the first time in undoped H2O and D2O; the ice Ih/II/XI triple point is also identified.