Calculations on polarization properties of alkali metal atoms using Dirac–Fock plus core polarization method

A semi-empirical atomic structure model method is developed in the framework of a relativistic case. This method starts from Dirac-Fock calculations using B-spline basis set. The core-valence electron correction is then treated in a semiempirical core polarization potential. As an application, the polarization properties of alkali metal atoms, including the static polarizabilities and long-range two-body dispersion coefficients, have been calculated. Our results are in good agreement with the results obtained from ab initio relativistic many-body perturbation method and the available experimental measurements.     

Effect of barium titanate nanoparticles of different particle sizes on electro-optic and dielectric properties of ferroelectric liquid crystal

A comparative study of two different particle sizes of ferroelectric barium titanate (BaTiO₃) nanoparticles as a dopant on the molecular structure, spontaneous polarization and dielectric behavior of a pure ferroelectric liquid crystal 6F₆T have been studied. It has been found that there is a remarkable decrease in isotropic temperature of both doped samples as compared to the pure 6F₆T sample. The spontaneous polarization also decreases for both the doped samples and the reduction is more pronounced in case of the dopant with large particle size. The dielectric spectroscopy confirms the presence of soft mode as well as Goldstone mode and also shows the decrease in the value of dielectric permittivity ?' as a function of frequency for both doped samples. The improvised properties of liquid crystal host doped with BaTiO₃ nanoparticles mainly depend upon the synthesis method of nanoparticles and also upon the particle size of dopant.     

Fluorinated Porous Poly(spirobifluorene) Via Direct C‒H Arylation: Characterization,Porosity, and Gas Uptake

Considering intrinsic properties of conjugated polyfluorenes and special functions of porous polymers, synthesis of fluorinated porous poly(spirobifluorene) via direct C?H arylation polycondensation is explored. Owing to the contorted structure and cross-linking nature, the obtained polymer FPSBF shows permanent porosities with Brunauer–Emmett–Teller specific surface area up to 700 m² g^?1 and exhibits a narrow pore size distribution with the dominant pore size at about 0.63 nm, which is more suitable for adsorption of small gas molecules. Based on the measured gas physisorption isotherms with pressure up to 1.13 bar, the obtained polymer shows good uptaking capacities for hydrogen (1.30 wt% at 1.0 bar and 77 K) and methane (4.80 wt% 1.0 bar and 273 K). Moreover, FPSBF has significant adsorption selectivity for CH₄ against N₂ and the estimated ideal adsorption selectivity ratio is up to 30/1 at 1.0 bar and 273 K, which makes the material possess potential application in gas separation.     

Synthesis and Polymerization of Spiro Oxyphosphoranes

Novel methods of synthesis of spiro acyloxyphosphoranes are described emphasizing the significance of the first isolated instance of these new species. Then, the no-catalyst alternating copolymerizations of the combinations of cyclic phosphorus(III) compounds (serving as nucleophilic monomer, M_N) with acrylic acid derivatives and with α-keto acids (electrophilic monomer, M_E) are mentioned. These copolymerizations proceed without added initiator. Spiro oxyphosphoranes play an important role in the copolymerization scheme in the equilibrium with the ⁺M_N - M_E ^? zwitterion, the key intermediate of the copolymerization. Finally, new reactions of spiro acyloxyphosphoranes with nucleophiles, alcoholysis and aminolysis polymerizations are presented.     

PHOTOELECTRON SPECTROSCOPY STUDY OF AMMONIA-INDUCED CHANGES IN ELECTROSTATICALLY-ASSEMBLED CONJUGATED POLYMER FILMS

ABSTRACT

Exposure of electrostatically assembled polyelectrolyte films comprised of the anionic carboxylic conjugated polymer poly[2-(3-thienyl)-ethanolhydroxycarbonylmethyl-urethane], hereafter referred to as H-PURET, and polycations such as poly(diallyldimethylammonium) chloride, here after referred to as PDADMAC, to aqueous ammonia vapor leads to dra matic changes in the ultraviolet-visible absorption spectrum. In the case of H-PURET/PDADMAC, a shift from 442 to 494 nm is observed upon overnight ammonia exposure. X-ray photoelectron spectroscopy has been used to investigate the mechanism of the changes in optical properties. The C1s, O1s and S2p core levels exhibit negligible ammonia-induced changes. Two N1s peaks are observed in virgin H-PURET/PDADMAC assemblies, and ammonia exposure causes the nitrogen peak corresponding to the H-PURET side chain to become more intense relative to that of the PDADMAC layer. This selective change in the N1s feature suggests that ammonia interacts with the polythiophene side-chain, presumably by deprotonating the fraction of carboxylic acid groups that remain in the H-PURET layer. This deprotonation apparently leads to structural or single chain conformational changes in the conjugated polymer layers that alter the electronic absorption spectrum.     

Molecular Assembly by Sequential Ionic Adsorption of Nanocrystalline TiO2 and a Conjugated Polymer

Abstract

Cationic nanocrystalline TiO₂ particles have been synthesized for which the size and composition of the nanoparticles were analyzed by a transmission emission microscopy and energy dispersive x‐ray spectrometer (EDXS). Multilayered films have been fabricated by sequential adsorption of TiO₂ nanoparticles and poly(3‐thiophene acetic acid) (PTAA). Each layer of the nanoparticles and PTAA in the thin film has also been characterized by x‐ray photoelectron spectroscopy, atomic force microscopy, and UV‐visible spectroscopy. These types of multilayered nanocomposite films may find applications in the fabrication of efficient light harvesting photovoltaic cells.     

Benzyl Bromide Functionalized Poly(Phenyleneethynylene)s as Macroinitiators in the Atom Transfer Radical Polymerization of Methyl Methacrylate

Abstract

The behavior of benzyl bromide functionalized poly(phenyleneethynylene)s as macroinitiators in the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) was investigated. The ¹H NMR observation of the ATRP using the exclusively para‐linked poly(phenyleneethynylene) macroinitiator PPE1A, and the low molecular weight initiator R‐BzBr, respectively, revealed lower reactivity for the macroinitiator. Comparison of graft copolymers, which were obtained from ATRP of MMA with PPE1A and the partially meta‐linked poly(phenyleneethynylene) PPE1B, showed higher reactivity in the case of PPE1B, expressed by a larger degree of polymerization in the PMMA side chains, as well as higher initiatior efficiency. This might be caused by better solubility of the less symmetric PPE1B. Investigation of the graft copolymers PPE2A and PPE2B was carried out by means of ¹H NMR spectroscopy, gel permeation chromatography (GPC) as well as UV/vis spectroscopy. Impairment of the delocalized π‐electron system of the conjugated polymers during the ATRP was not detectable.