Structural Transitions of Nitrogen Confined in Slit Graphite Pores

The structure of ordered phases that are formed when nitrogen is confined in slit graphite pores of height h is investigated using Monte Carlo simulations. The pore wall consists of a single-structured graphite sheet. Canonical ensemble simulations are carried out for temperatures ranging from 15 to 70Kwith layer density distributions, in-plane, out-of-plane angular distributions and snapshots evaluated at different temperatures. At each pore height the pore densities are obtained from independent grand ensemble simulations. At the smallest pore height studied (h)7 ��), where a single layer of molecules is accommodated at the center of the pore, the orientations are predominantly wall parallel, forming a biaxially incommensurate herringbone structure.Whentwo or more fluid layers are formed in the slit pore, the orientation of molecules adsorbed next to the wall can exist in either the herringbone or hexagonal phases. In all the multilayered cases studied, with the exception of the h ) 10 �� pore, where both wall layers form a commensurate herringbone structure, the low-temperature wall structures are incommensurate, possessing 6-fold hexagonal symmetry. The presence of the pinwheel structures, which were observed at low temperatures in the h ) 12 �� and h ) 14 �� pores, is determined by the pore height or the proximity and/or density of the adjacent fluid layers when inner layers are present.

Thermal Lipid Order���Disorder Transitions in Mixtures of Cationic Cholesteryl Lipid Analogues and Dipalmitoyl Phosphatidylcholine Membranes

Two types of cationic cholesteryl amphiphiles, one where the headgroup is attached to the steroid by an ester linkage and the second by an ether linkage, were synthesized. A third type of cholesteryl lipid bearing an oligoethylene glycol segment was also prepared. Each of these synthetic lipids generated vesicle-like aggregates with closed inner aqueous compartments from their aqueous suspensions. We examined their interaction with L-��-dipalmitoyl phosphatidylcholine (DPPC) membranes using fluorescence anisotropy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). When included in membranes, the synthetic cholesteryl lipids were found to quench the chain motion of the acyl chains of DPPC. This suggests that these cationic cholesteryl derivatives act as filler molecules despite modification at the headgroup level from the molecular structure of natural cholesterol. Careful analyses of DSC and fluorescence anisotropy data suggest that the nature of perturbation induced by each of these cationic cholesterol derivatives is dependent on the details of their molecular structure and provides significant information on the nature of interaction of these derivatives with phospholipid molecules. In general, amphiphiles that support structured water at the interfacial region tend to rigidify the fluid phase more than others. Importantly, these cholesteryl amphiphiles behave less like cholesterol in that their incorporation in DPPC not only abolishes the phase transition but also depresses the phase transition temperature.

Phase transitions in the anchored organic bilayers of long-chain alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4; n=12, 16, 18

The single perovskite slab alkylammonium lead iodides (CnH2n+1NH3)(2)PbI4, n = 12, 16, 18, display two phase transitions, just above room temperature, associated with changes in the alkylammonium chains. We have followed these two phase transitions using scanning calorimetry, X-ray powder diffraction, and IR and Raman spectroscopies. We find the first phase transition to be associated with symmetry changes arising from a dynamic rotational disordering of the ammonium headgroup of the chain whereas the second transition, the melting of the chains in two dimensions, is characterized by an increased conformational disorder of the methylene units of the alkyl chains. We examine these phase transitions in light of the interesting optical properties of these materials, as well as the relevance of these systems as models for phase transitions in lipid bilayers.

Infrared studies of the phase transitions of alkylammonium halides, RNH3X, and bis-(alkylammonium) tetrahalogenometallates(II), (RNH3)2MX4, (R = alkyl, M = metal, X = Cl or Br)

Internal vibration modes of bis-(alkylammonium) tetrachlorometallates(II) and the corresponding alkylammonium chlorides have been studied through their phase transitions using infrared spectroscopy. The studies show that the vibrational states of alkylammonium ions change markedly through the phase transitions. Spectra of the analogous tetrabromometallates and alkylammonium bromides also confirm this behaviour. There is appreciable motion of the alkylammonium ions in the high-temperature phases; thus, CH3NH+3 ions are essentially undistorted in these phases. The low-temperature, ordered phases show evidence of stronger hydrogen bonding of the cations and for the presence of C���N torsional modes.

Spin State Selective Excitation of Single Quantum Transitions Using Multiple Quantum Spectroscopy- an Aid to Analyse Complex Proton NMR spectra of Oriented Molecules

NMR spectra of molecules oriented in liquid-crystalline matrix provide information on the structure and orientation of the molecules. Thermotropic liquid crystals used as an orienting media result in the spectra of spins that are generally strongly coupled. The number of allowed transitions increases rapidly with the increase in the number of interacting spins. Furthermore, the number of single quantum transitions required for analysis is highly redundant. In the present study, we have demonstrated that it is possible to separate the subspectra of a homonuclear dipolar coupled spin system on the basis of the spin states of the coupled heteronuclei by multiple quantum (MQ)���single quantum (SQ) correlation experiments. This significantly reduces the number of redundant transitions, thereby simplifying the analysis of the complex spectrum. The methodology has been demonstrated on the doubly 13C labeled acetonitrile aligned in the liquid-crystal matrix and has been applied to analyze the complex spectrum of an oriented six spin system.

Time-dependent transitions with time-space noncommutativity and its implications in quantum optics

We study the time-dependent transitions of a quantum-forced harmonic oscillator in noncommutative R(1,1) perturbatively to linear order in the noncommutativity theta. We show that the Poisson distribution gets modified, and that the vacuum state evolves into a `squeezed' state rather than a coherent state. The time evolutions of uncertainties in position and momentum in vacuum are also studied and imply interesting consequences for modeling nonlinear phenomena in quantum optics.

Anderson transitions in Ln1-x Sr x CoO3 (Ln���Pr or Nd)

Electrical conductivity measurements show that Ln1-x Sr x CoO3, (Ln = Pr or Nd) undergoes a non-metal-metal transition when x���0 3. The d.c. conductivity of compositions with 0<x<0.l obeys the T���1/4law up to 400 K and the a.c. conductivity data follow the ���� law with �� in the range 0.6���0.8. Surprisingly, however, �� seems to increase with increasing temperature. Thermopower measurements show clear evidence for a change in the mechanism of conduction (around 350 K) from variable range hopping to transport at E c. All these transport properties suggest that Co4+ ions in Ln1-x Sr x CoO3 (0<x<0.1), considered as moving in a lattice of Co3+, form a degenerate gas and that the states at the Fermi energy are Anderson localized.

Raman signatures of pressure induced electronic topological and structural transitions in Bi2Te3

We report Raman signatures of electronic topological transition (ETT) at 3.6 GPa and rhombohedral (alpha-Bi2Te3) to monoclinic (beta-Bi2Te3) structural transition at similar to 8 GPa. At the onset of ETT, a new Raman mode appears near 107 cm(-1) which is dispersionless with pressure. The structural transition at similar to 8 GPa is marked by a change in pressure derivative of A(1g) and E-g mode frequencies as well as by appearance of new modes near 115 cm(-1) and 135 cm(-1). The mode Grilneisen parameters are determined in both the alpha and beta-phases. (C) 2011 Elsevier Ltd. All rights reserved.

Temperature gradient induced phase transitions and morphological changes in diamond thin film

The diamond films were deposited onto a wurtzite gallium nitride (GaN) thin film substrate using hot-filament chemical vapor deposition (HFCVD). During the film deposition a lateral temperature gradient was imposed across the substrate by inclining the substrate. As grown films predominantly showed the hexagonal phase, when no inclination was applied to the substrate. Tilting the substrate with respect to the heating filament by 6 degrees imposed a lateral temperature gradient across the substrate, which induced the formation of a cubic diamond phase. Diamond grains were predominantly oriented in the (100) direction. However, a further increase in the substrate tilt angle to 12 degrees, resulted in grains oriented in the (111) direction. The growth rate and hence the morphology of diamond grains varied along the inclined substrate. The present study focuses on the measurements of dominant phase formation and crystal orientation with varying substrate inclination using orientation-imaging microscopy (OIM). This technique enables direct examination of individual diamond grains and their crystallographic orientation. (C) 2012 Elsevier B.V. All rights reserved.