Stable molecular configuration in crystalline carboxylic acids

The stable (lower enthalpy) molecular configurations of propionic, butyric, Jeric and lauric acids in the crystalline state have been examined via their atom-atom potentials. It was found that the cis configuration is more stable than the trans configuration for propionic, butyric and valeric acids, and that the trans configuration is more stable than the cis configuration for lauric acid, in accord with a previous IR spectral analysis. The potential energy of benzoic acid was recalculated using the positions of atoms given by Speakman, and indicates that the A form is more stable than the B form, in agreement with the results of previous work.     

Kinetic model of polymorphic transitions in molecular crystals

A polychromous model in the form of an integral equation of first kind is suggested for autocatalytic polymorphic transitions of arbitrary order in molecular crystals. The model relates the observed heat absorption to the distribution of the volume of the crystalline substance over the concentrations of the initial and final modifications. The activation energy of the polymorphic transition has been calculated. The inverse problem of reconstructing the distribution function from experimental data has been solved. The model is in good quantitative and qualitative agreement with calorimetric data.     

Phase transitions of adsorbed carboxylic acids on zinc oxide and of zinc soaps. Infrared and X-ray diffraction investigations

Summary The reaction between carboxylic acids in benzene solution and suspended zinc oxide particles was investigated by means of infrared spectrometry. The results show how the carboxyl groups react with the zinc oxide forming zinc carboxylate groups at the chemisorption. The chemisorbed acid forms a multilayer at the surface, which gives a new explanation of the protective action of adsorbed acids against flocculation of the particles in nonpolar solvents. The temperature-dependence of the spectra showed transitions at the same temperatures and of the same kind as the corresponding zinc carboxylates, whose spectra were also recorded. The zinc soaps exhibited thermotropic behaviour, and lyotrophy is suggested as the explanation of the multilayer formation.

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Zusammenfassung Mit Hilfe der Infrarotspektrometrie wurde die Einwirkung von Stearins?ure und ?ls?ure auf Zinkoxid untersucht, das in Benzol suspendiert worden war. Durch Carboxylatbildung wird eine multimolekulare Schicht der S?uren auf der Oberfl?che der Zinkpartikel ausgebildet. Die Partikel werden dadurch von der Flokkulation in nichtpolaren L?sungsmitteln geschützt. Die Temperaturabh?ngigkeit der Spektren entspricht der der Zinkcarboxylate.

     

Phase transitions in ferroelectric liquid crystals in a restricted geometry

Abstract

Using a wedge type cell, we have studied the S_A–S*_c, S*_c–S_c and S_A–S_c phase transition lines in the ferroelectric liquid crystals 4-(2-methylbutyl)phenyl 4′-n-octylbiphenyl-4-carboxylate (CE-8) and 2-methylbutyl 4-(4-decyloxy-benzylidene)aminocinnamate (DOBAMBC) as a function of cell thickness in the planar geometry. The phase diagram is similar to the one observed using an external magnetic field. A surface induced re-entrant-like phenomenon is also observed. The experimental results are compared with the predictions of a Landau model with surface anchoring and a qualitative agreement was found. The results show that whereas disclination lines are not important for the S_A–S*_c and S_A–S_c transition lines, these defects have to be taken into account when evaluating the S*_c→S_c transition line. The form of the phase diagram has some important implications for the performance of surface stabilized ferroelectric liquid crystal cells used in electrooptic devices.     

Phase transitions of methane using molecular dynamics simulations

Using a short ranged Lennard-Jones interaction and a long ranged electrostatic potential, CH4 under high pressure was modeled. Molecular dynamics simulations on small clusters (108 and 256 molecules) were used to explore the phase diagram. Regarding phase transitions at different temperatures, our numerical findings are consistent with experimental results to a great degree. In addition, the hysteresis effect is displayed in our results.     

两亲性分子聚集体的相变及其协同性

两亲性分子聚集体是一类重要的软物质,它们有着丰富而复杂的相行为.本文主要从两个方面综述了作者所在的研究组在两亲性分子聚集体相变研究方面的工作进展.(1)磷脂相关体系相变热力学:归纳了多种小分子(二甲基亚砜、甘油、海藻糖、尿素等)对于磷脂体系相行为的调控,比较并讨论了固醇类分子和葡萄糖神经酰胺分子诱导磷脂分子形成液态有序相的能力,还介绍了计算机模拟磷脂相行为的工作进展.(2)两亲性分子聚集体相变的协同性:先介绍了相变协同性(即分子头部、尾部、界面等基团在相变过程中的一致性)问题的提出,然后通过双十八烷基二甲基溴化铵分子和硬脂酰溶血卵磷脂两个体系的研究实例,说明两亲性分子聚集体相变过程中存在着头尾不一致的现象.对这个问题的研究,将为我们打开挑战相态转变的一系列重大问题(如相变动力学、相态多型性、相态稳定性以及相变可逆性等)的新窗口.     

Phase transitions and the stability of atomic and molecular ions

Quantum phase transitions at absolute zero temperature can take place as some parameter in the Hamiltonian of the system is varied. For such transitions, crossing the phase boundary means that the quantum ground state changes in some fundamental way. For the Hamiltonian of N-electron atoms, this parameter is taken to be the nuclear charge. As the nuclear charge reaches a critical point, the quantum ground state changes its characters from being bound to being degenerate or absorbed by a continuum. We describe here a method to calculate the critical nuclear charge for which an atom can bind an extra electron to form a stable negative ion. The estimate of the critical nuclear charge will be used to explain and predict the stability of atomic negative ions. The method can be generalized to predict the stability of molecular negative ions. A detailed calculation for the critical parameters for two center molecular ions is also included.     

To the question on radiationless transitions in electronically excited zones of molecular crystals

A model is proposed describing the dynamics of radiationless transitions in the energy zones corresponding to excited electronic states in molecular crystals. In this model, the migration effect is explicitly reflected, which initially appears under pulse excitation of the systems with a periodical structure of a density distribution of states in separate parts of molecular crystals.     

Phase transitions during heating of melt-drawn ultrahigh molecular weight polyethylenes having different molecular characteristics

Changes in the crystalline structure during heating of melt-drawn ultrahigh molecular weight polyethylenes (UHMW-PEs) having different molecular characteristics were analyzed by in situ wide-angle X-ray diffraction measurements. A phase transition from the orthorhombic into the hexagonal phase was observed for all samples, but the perfection was enhanced and the possible temperature window for the hexagonal phase was greater for the sample containing only a higher molecular weight component. In contrast, an increase in retractive stress during heating was confirmed for the sample containing a lower molecular weight component, reflecting melting of the folded-chain crystal (FCC). Differential scanning calorimetry and transmission electron microscopy revealed the dependency of the molecular characteristics of the sample on the resultant morphologies. These results demonstrate that the existence of FCC determines both the quality and the width of the temperature window for the hexagonal phase during heating of melt-drawn UHMW-PEs.     

Supramolecular liquid crystals formed by hydrogen bonding between a benzocrown-bearing stilbazole and carboxylic acids

The mesomorphism of hydrogen bonded complexes formed between 4'-carboxybenzo-15-crown-5 stilbazolyl ester (CBCSE) as proton acceptor and carboxylic acids as proton donors is discussed. CBCSE is a monotropic mesogen, forming a nematic phase upon quench cooling. A total of 32 hydrogen bonded complexes has been studied. Hydrogen bonding with carboxylic acids stabilizes the nematic phase, and/or induces a smectic A (SmA) phase. CBCSE forms 1:1 complexes (molar ratio) with alkanoic acids (fatty acids) and 2:1 complexes with alkanedioic acids. None of these proton donors is a mesogen itself, but the hydrogen bonded complexes are. The influence of the chain or spacer length on the transition temperatures is discussed. Besides the homologous series of the alkanoic and alkanedioic acids, the following carboxylic acids were used in this study: diglycolic acid, pyridine-2,6-dicarboxylic acid, 4-dodecyloxybenzoic acid, 3,4-bis(dodecyloxy)benzoic acid, 2,3,4-tris(dodecyloxy)benzoic acid and 3,4,5-tris(dodecyloxy)benzoic acid, phthalic acid, isophthalic acid and terephthalic acid.     

Supramolecular liquid crystals formed by hydrogen bonding between a benzocrown-bearing stilbazole and carboxylic acids

The mesomorphism of hydrogen bonded complexes formed between 4'-carboxybenzo-15-crown-5 stilbazolyl ester (CBCSE) as proton acceptor and carboxylic acids as proton donors is discussed. CBCSE is a monotropic mesogen, forming a nematic phase upon quench cooling. A total of 32 hydrogen bonded complexes has been studied. Hydrogen bonding with carboxylic acids stabilizes the nematic phase, and/or induces a smectic A (SmA) phase. CBCSE forms 1:1 complexes (molar ratio) with alkanoic acids (fatty acids) and 2:1 complexes with alkanedioic acids. None of these proton donors is a mesogen itself, but the hydrogen bonded complexes are. The influence of the chain or spacer length on the transition temperatures is discussed. Besides the homologous series of the alkanoic and alkanedioic acids, the following carboxylic acids were used in this study: diglycolic acid, pyridine-2,6-dicarboxylic acid, 4-dodecyloxybenzoic acid, 3,4-bis(dodecyloxy)benzoic acid, 2,3,4-tris(dodecyloxy)benzoic acid and 3,4,5-tris(dodecyloxy)benzoic acid, phthalic acid, isophthalic acid and terephthalic acid.     

Phase transitions and molecular properties of new divinyl and diepoxy compounds

The aim of this paper is to compare some physical properties of six new divinyl and diepoxy compounds. The compounds differ in the length of the rigid central segments. Optical observations and differential scanning calorimetry confirmed the existence of a mesophase in five compounds and enabled the determination of the phase transition temperatures. The wide angle X-ray scattering (WAXS) measurements of samples aligned in a magnetic field and the optical observations allowed the identification of the mesophase types. In four compounds a nematic mesophase was detected during both heating and cooling. In one case two higher ordered phases were observed during cooling. The analysis of WAXS images and the positions and shapes of the scattering intensity peaks suggests a smectic B-crystal E transition. Using the data obtained in WAXS measurements carried out in the nematic phase, the lengths of the molecules and the average nearest neighbour distances were estimated. The average intermolecular distances and the layer spacings were also estimated for the SmB and E phases. The lengths of the molecules were also calculated by means of theoretical ab initio methods. The results obtained are in very good agreement with the experimental data.     

Plenary Lecture. Phase transitions and critical phenomena in polar smectic A liquid crystals

Since the discovery of a phase transition between two polymorphic forms of the smectic A phase, there has been a considerable amount of experimental as well as theoretical work on strongly polar materials exhibiting different smectic A phases. These studies have led to the observation of a variety of new phase transitions and critical phenomena which are rarely encountered in any other area of condensed matter physics. We review briefly some of these important results.     

Plenary Lecture. Phase transitions and critical phenomena in polar smectic A liquid crystals

Since the discovery of a phase transition between two polymorphic forms of the smectic A phase, there has been a considerable amount of experimental as well as theoretical work on strongly polar materials exhibiting different smectic A phases. These studies have led to the observation of a variety of new phase transitions and critical phenomena which are rarely encountered in any other area of condensed matter physics. We review briefly some of these important results.     

Esterification of polymeric carboxylic acids

Polymers containing pendant carboxyl groups have been essentially completely esterified with little apparent change in molecular weight by the use of one of the following reagents: (1) trialkyl orthoesters, (2) dimethylformamide dialkyl acetals, (3) tertiary amines followed by alkyl halides, (4) quaternary ammonium hydroxide followed by alkyl halides. The use of some of these methods permits preparation of certain polymers that were previously not readily accessible.