Liquid polymorphism, order-disorder transitions and anomalous behavior: A Monte Carlo study of the Bell-Lavis model for water

The Bell-Lavis model for liquid water is investigated through numerical simulations. The lattice-gas model on a triangular lattice presents orientational states and is known to present a highly bonded low density phase and a loosely bonded high density phase. We show that the model liquid-liquid transition is continuous, in contradiction with mean-field results on the Husimi cactus and from the cluster variational method. We define an order parameter which allows interpretation of the transition as an order-disorder transition of the bond network. Our results indicate that the order-disorder transition is in the Ising universality class. Previous proposal of an Ehrenfest second order transition is discarded. A detailed investigation of anomalous properties has also been undertaken. The line of density maxima in the HDL phase is stabilized by fluctuations, absent in the mean-field solution. (C) 2009 American Institute of Physics. [doi:10.1063/1.3253297]

Order-Disorder Transitions Govern Kinetic Cooperativity and Allostery of Monomeric Human Glucokinase

Glucokinase (GCK) catalyzes the rate-limiting step of glucose catabolism in the pancreas, where it functions as the body's principal glucose sensor. GCK dysfunction leads to several potentially fatal diseases including maturity-onset diabetes of the young type II (MODY-II) and persistent hypoglycemic hyperinsulinemia of infancy (PHHI). GCK maintains glucose homeostasis by displaying a sigmoidal kinetic response to increasing blood glucose levels. This positive cooperativity is unique because the enzyme functions exclusively as a monomer and possesses only a single glucose binding site. Despite nearly a half century of research, the mechanistic basis for GCK's homotropic allostery remains unresolved. Here we explain GCK cooperativity in terms of large-scale, glucose-mediated disorder-order transitions using 17 isotopically labeled isoleucine methyl groups and three tryptophan side chains as sensitive nuclear magnetic resonance (NMR) probes. We find that the small domain of unliganded GCK is intrinsically disordered and samples a broad conformational ensemble. We also demonstrate that small-molecule diabetes therapeutic agents and hyperinsulinemia-associated GCK mutations share a strikingly similar activation mechanism, characterized by a population shift toward a more narrow, well-ordered ensemble resembling the glucose-bound conformation. Our results support a model in which GCK generates its cooperative kinetic response at low glucose concentrations by using a millisecond disorder-order cycle of the small domain as a "time-delay loop," which is bypassed at high glucose concentrations, providing a unique mechanism to allosterically regulate the activity of human GCK under physiological conditions.

Structural, electronic, and magnetic entropy contributions of the orbital order-disorder transition in LaMnO(3)

Measurements of X-ray diffraction, electrical resistivity, and magnetization are reported across the Jahn-Teller phase transition in LaMnO(3). Using a thermodynamic equation, we obtained the pressure derivative of the critical temperature (T(JT)), dT(JT)/dP = -28.3 K GPa(-1). This approach also reveals that 5.7(3)J(mol K)(-1) comes from the volume change and 0.8(2)J(mol K)(-1) from the magnetic exchange interaction change across the phase transition. Around T(JT), a robust increase in the electrical conductivity takes place and the electronic entropy change, which is assumed to be negligible for the majority of electronic systems, was found to be 1.8(3)J(mol K)(-1).

Diffusionless first-order phase transitions in systems with frozen configurational degrees of freedom

We consider systems that can be described in terms of two kinds of degree of freedom. The corresponding ordering modes may, under certain conditions, be coupled to each other. We may thus assume that the primary ordering mode gives rise to a diffusionless first-order phase transition. The change of its thermodynamic properties as a function of the secondary-ordering-mode state is then analyzed. Two specific examples are discussed. First, we study a three-state Potts model in a binary system. Using mean-field techniques, we obtain the phase diagram and different properties of the system as a function of the distribution of atoms on the different lattice sites. In the second case, the properties of a displacive structural phase transition of martensitic type in a binary alloy are studied as a function of atomic order. Because of the directional character of the martensitic-transition mechanism, we find only a very weak dependence of the entropy on atomic order. Experimental results are found to be in quite good agreement with theoretical predictions.

Driving rate effects in avalanche-mediated first-order phase transitions

We study the driving-rate and temperature dependence of the power-law exponents that characterize the avalanche distribution in first-order phase transitions. Measurements of acoustic emission in structural transitions in Cu-Zn-Al and Cu-Al-Ni are presented. We show how the observed behavior emerges within a general framework of competing time scales of avalanche relaxation, driving rate, and thermal fluctuations. We confirm our findings by numerical simulations of a prototype model.

Sequential partitioning: an alternative to understanding size distributions of avalanches in first-order phase transitions

We study the problem of the partition of a system of initial size V into a sequence of fragments s1,s2,s3 . . . . By assuming a scaling hypothesis for the probability p(s;V) of obtaining a fragment of a given size, we deduce that the final distribution of fragment sizes exhibits power-law behavior. This minimal model is useful to understanding the distribution of avalanche sizes in first-order phase transitions at low temperatures.

Effects of polydispersity on the order-disorder transition of diblock copolymer melts

The effect of polydispersity on an AB diblock copolymer melt is investigated using latticebased Monte Carlo simulations. We consider melts of symmetric composition, where the B blocks are monodisperse and the A blocks are polydisperse with a Schultz-Zimm distribution. In agreement with experiment and self-consistent field theory (SCFT), we find that polydispersity causes a significant increase in domain size. It also induces a transition from flat to curved interfaces, with the polydisperse blocks residing on the inside of the interfacial curvature. Most importantly, the simulations show a relatively small shift in the order-disorder transition (ODT) in agreement with experiment, whereas SCFT incorrectly predicts a sizable shift towards higher temperatures.

Joint Experimental and Theoretical Analysis of Order Disorder Effects in Cubic BaZrO(3) Assembled Nanoparticles under Decaoctahedral Shape

Periodic first-principles calculations based on density functional theory at the B3LYP level has been carried out to investigate the photoluminescence (PL) emission of BaZrO(3) assembled nanoparticles at room temperature. The defect created in the nanocrystals and their resultant electronic features lead to a diversification of electronic recombination within the BaZrO(3) band gap. Its optical phenomena are discussed in the light of photoluminescence emission at the green-yellow region around 570 nm. The theoretical model for displaced atoms and/or angular changes leads to the breaking of the local symmetry, which is based on the refined structure provided by Rietveld methodology. For each situation a band structure, charge mapping, and density of states were built and analyzed. X-ray diffraction (XRD) patterns, UV-vis measurements, and field emission scanning electron microscopy (FE-SEM) images are essential for a full evaluation of the crystal structure and morphology.

Intense violet-blue photoluminescence in BaZrO3 powders: A theoretical and experimental investigation of structural order-disorder

Intense violet-blue photoluminescence (PL) emission at room temperature was verified in BaZrO3 (BZO) powders with structural order-disorder. Ab-initio calculations, ultraviolet-visible absorption spectroscopy and PL were performed. Theoretical results showed that the local disorder in the network-formed Zr clusters present an important role in the formation of hole-electron pair. The experimental data and theoretical results are in agreement, indicating that the PL emission in BZO powders can be related to the structural order-disorder degree in the lattice. (C) 2008 Elsevier B.V. All rights reserved.

Order-disorder degree of self-assembled clusters: Influence on photoluminescence emission and morphology of BaxSr1-xTiO3 nanocrystals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Critical temperature for first-order phase transitions in confined systems

We consider the Euclidean D-dimensional -lambda vertical bar phi vertical bar(4)+eta vertical bar rho vertical bar(6) (lambda,eta > 0) model with d (d <= D) compactified dimensions. Introducing temperature by means of the Ginzburg-Landau prescription in the mass term of the Hamiltonian, this model can be interpreted as describing a first-order phase transition for a system in a region of the D-dimensional space, limited by d pairs of parallel planes, orthogonal to the coordinates axis x(1), x(2),..., x(d). The planes in each pair are separated by distances L-1, L-2, ... , L-d. We obtain an expression for the transition temperature as a function of the size of the system, T-c({L-i}), i = 1, 2, ..., d. For D = 3 we particularize this formula, taking L-1 = L-2 = ... = L-d = L for the physically interesting cases d = 1 (a film), d = 2 (an infinitely long wire having a square cross-section), and for d = 3 (a cube). For completeness, the corresponding formulas for second-order transitions are also presented. Comparison with experimental data for superconducting films and wires shows qualitative agreement with our theoretical expressions.

Intense violet-blue photoluminescence in BaZrO3 powders: A theoretical and experimental investigation of structural order-disorder

Intense violet-blue photoluminescence (PL) emission at room temperature was verified in BaZrO3 (BZO) powders with structural order-disorder. Ab-initio calculations, ultraviolet-visible absorption spectroscopy and PL were performed. Theoretical results showed that the local disorder in the network-formed Zr clusters present an important role in the formation of hole-electron pair. The experimental data and theoretical results are in agreement, indicating that the PL emission in BZO powders can be related to the structural order-disorder degree in the lattice. (C) 2008 Elsevier B.V. All rights reserved.

Contribution of structural order-disorder to the room-temperature photoluminescence of lead zirconate titanate powders

Intense and broad visible photoluminescent (PL) band was observed at room temperature in structurally disordered PbZr0.53Ti0.47O3 powders. The lead zirconate titanate PbZr0.53Ti0.47O3 powders prepared by the polymeric precursor method and heat treated at different temperatures were structurally characterized at long range by means of X-ray diffraction. The PL was measured at room temperature samples heat treated at different temperatures. Experimental measurements and quantum-mechanical calculations showed that the high structural order and the high structural disorder in PbZr0.53Ti0.47O3 lattice are not favorable to the intense PL emission. Only samples containing simultaneous structural order and disorder in their lattice present the intense visible PL emission at room temperature. (C) 2007 Published by Elsevier B.V.

The role of structural order-disorder for visible intense photoluminescence in the BaZr0.5Ti0.5O3 thin films

The nature of the intense visible room temperature photoluminescence of BaZr0.5Ti0.5O3 non-crystalline thin films is discussed in the light of experimental results and theoretical calculations. The photoluminescence measurements reveal that the emission intensity changes with the degree of disorder in the BaZr0.5Ti0.5O3 lattice. First principles quantum mechanical techniques, based on density functional theory at B3LYP level, have been employed to study the electronic structure of a crystalline model and of structurally disordered models in order to detect the influence of disorder on the electronic structure. An analysis of the electronic charge distribution reveals local polarization in the disordered structures. The relevance of the present theoretical and experimental results on the photoluminescence behavior of BZT is discussed. (C) 2005 Elsevier B.V. All rights reserved.