Energy landscape view of phase transitions and slow dynamics in thermotropic liquid crystals

Thermotropic liquid crystals are known to display rich phase behavior on temperature variation. Although the nematic phase is orientationally ordered but translationally disordered, a smectic phase is characterized by the appearance of a partial translational order in addition to a further increase in orientational order. In an attempt to understand the interplay between orientational and translational order in the mesophases that thermotropic liquid crystals typically exhibit upon cooling from the high-temperature isotropic phase, we investigate the potential energy landscapes of a family of model liquid crystalline systems. The configurations of the system corresponding to the local potential energy minima, known as the inherent structures, are determined from computer simulations across the mesophases. We find that the depth of the potential energy minima explored by the system along an isochor grows through the nematic phase as temperature drops in contrast to its insensitivity to temperature in the isotropic and smectic phases. The onset of the growth of the orientational order in the parent phase is found to induce a translational order, resulting in a smectic-like layer in the underlying inherent structures; the inherent structures, surprisingly, never seem to sustain orientational order alone if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. The Arrhenius temperature dependence of the orientational relaxation time breaks down near the isotropic-nematic transition. We find that this breakdown occurs at a temperature below which the system explores increasingly deeper potential energy minima.

Interfacial microrheology as a tool to study viscoelastic transitions in nanoconfined soft matter

We present a method to perform in situ microrheological measurements on monolayers of soft materials undergoing viscoelastic transitions under compression. Using the combination of a Langmuir trough mounted on the inverted microscope stage of a laser scanning confocal microscope we track the motion of individual fluorescent quantum dots partly dispersed in monolayers spread at the air-water interface. From the calculated mean square displacement of the probe particles and extending a well established scheme of the generalized Stokes-Einstein relation in bulk to the interface we arrive at the viscoelastic modulus for the respective monolayers as a function of surface density. Measurements on monolayers of glassy as well as nonglassy polymers and a standard fatty acid clearly show sensitivity of our technique to subtle variations, in the viscoelastic properties of the highly confined materials under compression. Evidence for possible spatial variations of such viscoelastic properties at a given surface density for the fatty acid monolayer is also provided.

Interfacial microrheology as a tool to study viscoelastic transitions in nanoconfined soft matter

We present a method to perform in situ microrheological measurements on monolayers of soft materials undergoing viscoelastic transitions under compression. Using the combination of a Langmuir trough mounted on the inverted microscope stage of a laser scanning confocal microscope we track the motion of individual fluorescent quantum dots partly dispersed in monolayers spread at the air-water interface. From the calculated mean square displacement of the probe particles and extending a well established scheme of the generalized Stokes-Einstein relation in bulk to the interface we arrive at the viscoelastic modulus for the respective monolayers as a function of surface density. Measurements on monolayers of glassy as well as nonglassy polymers and a standard fatty acid clearly show sensitivity of our technique to subtle variations, in the viscoelastic properties of the highly confined materials under compression. Evidence for possible spatial variations of such viscoelastic properties at a given surface density for the fatty acid monolayer is also provided.

Electronic-Transitions In Hydrogen-Bonded Dimers Of Carboxylic-Acids In The Vapor-Phase - An Electron-Energy Loss Spectroscopic Study

An electron energy loss spectroscopic study of the formic acid dimer has shown bands centred around 7.2, 8.5, 9.8, and 11.1 eV, of which the first and the third bands are assigned to n- rc* transitions and the other two to n-n* transitions; similar transitions are found in the acetic acid dimer.

PES studies of semiconductor - metal transitions in metal oxides

Semiconductor-Metal transitions in Ti2O3, VO2, V2O3 and Ti3O5 have been investigated employing X-ray and UV Photoelectron spectroscopy. The transitions are accompanied by significant changes in the 3d band of the transition metals as well as some of the core levels.

Studies on the phase transitions in thiourea

Thiourea (CS(NH2)2) is one of the few examples of molecular crystals exhibiting ferroelectric properties. The dielectric constant along the ferroelectric axis [100] shows maxima at 169, 177 and 202 K. An inflection point occurs at 170.5 KZ Following Goldsmith and White the phases are named as I (F.E. below 169 K), II (A.F.E. 169 K

Two-dimensional NMR spectroscopy of connected transitions by linear combination of flip angle dependent cosy: An alternative scheme for E.COSY

An alternative pulse scheme which simplifies and improves the recently proposed P.E.COSY experiment is suggested for the retention of connected or unconnected transitions in a coupled spin system. An important feature of the proposed pulse scheme is the improved phase characteristics of the diagonal peaks. A comparison of various experiments designed for this purpose, namely COSY-45, E.COSY, P.E.COSY and the present scheme (A.E.COSY), is also presented. The suppression of unconnected transitions and the measurement of scalar coupling constants and their relative signs are illustrated from A.E.COSY spectra of 2,3-dibromopropionic acid and 2-(2-thienyl)pyridine.

A bibliographical review of the high pressure studies of ferroelectric phase transitions

A brief review of the various high pressure studies on the phase transitions in ferroelectric crystals carried out over the past two decades is presented. The theoretical framework in which high pressure studies have to be viewed is given. The pressure data of ferroelectric crystals are organized in the form of tables. High pressure spectroscopic and structural studies are included. The review contains a bibliography of over two hundred references.

Pes study of spin-state transitions in d6 transition metal complexes and oxides

Transitions from the low-to the high-spin state in Fe2+ and Co3+ compounds have been examined by X-ray and UV photoelectron spectroscopy. It has been shown that the core-level bands in XPES, in particular the metal 3s band, as well as the valence bands, are diagnosis in the study of spin-state transitions.

Models for spin-state transitions in solids

The model for spin-state transitions described by Bari and Sivardiere (1972) is static and can be solved exactly even when the dynamics of the lattice are included; the dynamic model does not, however, show any phase transition. A coupling between the octahedra, on the other hand, leads to a phase transition in the dynamical two-sublattice displacement model. A coupling of the spin states to the cube of the sublattice displacement leads to a first-order phase transition. The most reasonable model appears to be a two-phonon model in which an ion-cage mode mixes the spin states, while a breathing mode couples to the spin states without mixing. This model explains the non-zero population of high-spin states at low temperatures, temperature-dependent variations in the inverse susceptibility and the spin-state population ratio, as well as the structural phase transitions accompanying spin-state transitions found in some systems.

Metal-insulator transitions in Cr-doped V2O3 by x-ray and ultraviolet photoelectron spectroscopy

X-ray and ultraviolet photoelectron spectroscopy have been employed to investigate the high temperature metal-insulator transitions in V2O3 and (V0.99Cr0.01)2O3. The high temperature transitions are associated with more gradual changes in the 3d bands compared to the low-temperature transitions

Jahn-Teller effect induced phase transitions in CsCuCl3

Occurence of the three Jahn-Teller effect induced phase transitions of CsCuCl3 at 423, 510 and 535 K has been established and the nature of the transitions examined by X-ray crystallography, far infrared spectroscopy and other techniques.

Infrared spectroscopic study of the phase transitions in CsNO3, RbNO3 and NH4NO3

Phase transitions of CsNO3 (II-I), RbNO3 (IV-III-II) and NH4NO3 (V-IV-III-II-I) have been studied by i.r. spectroscopy. The study has provided useful information on the changes in the dispositions of the ions during the phase transitions.

Infrared and Nuclear Quadrupole Resonance Studies of the Phase Transitions of Para-dichlorobenzene

The α→γ→α→β transitions of para-dichlorobenzene have been studied by employing infrared and n.q.r. spectroscopy as well as differential scanning calorimetry. The γ phase is associated with considerably higher values of some of the intramolecular vibration frequencies. The α→γ transition shows athermal nucleation behaviour as in martensitic transitions. Intermolecular vibration bands around 46 and 85 cm–1 present in γ and α phases disappear in the β phase. The α→β transition seems to be associated with some orientational disorder.

Jahn-Teller effect induced phase transitions in CsCuCl3

Occurence of the three Jahn-Teller effect induced phase transitions of CsCuCl3 at 423, 510 and 535 K has been established and the nature of the transitions examined by X-ray crystallography, far infrared spectroscopy and other techniques.