Search results for "bonding"

Ionic transport and heat capacity of glass-forming metalnitrate mixtures

1997

Abstract Ionic transport of the glass-forming metalnitrate mixtures [Ca(NO 3 ) 2 ] 0.44 [KNO 3 ] 0.56 (MKN), and [Mg(NO 3 ) 2 ] 0.44 [NaNO 3 ] 0.56 (MNN) was investigated near the glass transition using broadband spectroscopy of the complex conductivity to 300 MHz. The real part of the conductivity exhibits a transition from frequency independent to power law behavior as found in most ionic conductors. At high frequencies the frequency exponent approaches unity and becomes larger at low temperatures. In the real part of the dielectric constant, a relaxation step could be observed in CRN. A detailed evaluation of the results within the modulus formalism is presented. The imaginary part of t…

General occurrence of polar twisted minima in the ionic singlet excited surfaces of polyenes

1982

Except for a few cases, the lowest closed shell SCF solutions for the twisted geometries of polyenes involves delocalized nonpolarized MO’s, and represents a meaningless mixture of radicalar gound state and ionic excited states. Higher (quasi) solutions allow a realistic approach of the polarized ionic states. Orthogonality to the radicalar ground state may be imposed without important loss of energy. Further extensive CI does not modify significantly the situation. These statements are illustrated through ab initio calculations of butadiene and hexatriene. This approach allows us to show that slight distortions stablize polar minima even in ’’homosymmetric’’ molecules such as all‐trans hex…

Calculations of F centers in KNbO 3 ferroelectric crystals

1997

Semi-empirical method of the intermediate neglect of the differential overlap (INDO) combined with the supercell model is applied to the calculations of the F center optical properties in ferroelectric KNbO 3 perovskite crystals. It is shown that two electrons of the defect are weakly localized inside the O vacancy, unlike similar defects in ionic alkali halides, but are considerably spread over two nearest Nb atoms. For the orthorhombic phase stable at room temperatures three absorption bands are predicted to be at 2.72 eV, 3.04 eV and 3.11 eV, respectively. The first energy is close to the band at 2.7 eV observed in electron- irradiated crystals. In the high temperature, cubic phase only …

Hydrogen bond-stabilised N-alkylammonium resorcinarene halide cavitands

2010

A family of hydrogen bond-stabilised N-alkylammonium resorcinarene chloride and bromide cavitands were synthesised and characterised with 1H NMR and ESI mass spectrometry. The seven compounds exhibit interestingly either self-inclusion or guest complexation in the solid state evidenced by single crystal X-ray diffraction. The four dimers show self-inclusion of the upper rim propyl chains and consist of two hydrogen-bonded resorcinarene tetracations and six halide anions, while the remaining two halide anions are located in between the dimers linking them via hydrogen bonding. Small solvent molecules such as dichloromethane, methanol, n-butanol or chloroform are complexed into the resorcinar…

Gaining insight in the behaviour of imidazolium-based ionic liquids as additives in reversed-phase liquid chromatography for the analysis of basic co…

2015

In reversed-phase liquid chromatography in the absence of additives, cationic basic compounds give rise to broad and asymmetrical peaks as a result of ionic interactions with residual free silanols on silica-based stationary phases. Ionic liquids (ILs), added to the mobile phase, have been suggested as alternatives to amines to block the activity of silanols. However, the dual character of ILs should be considered: both cation and anion may be adsorbed on the stationary phase, thereby creating a double asymmetrical layer positively or negatively charged, depending on the relative adsorption of both ions. In this work, a study of the performance of six imidazolium-based ILs (the chlorides an…

Determination of the Stability Constants of the Acetate Complexes of the Actinides Am(III), Th(IV), Np(V), and U(VI) Using Capillary Electrophoresis-…

2019

Capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) was used to determine the stability constants of the actinides Am(III), Th(IV), Np(V), and U(VI) at an ionic strength of I = 0.3 M. The obtained stability constants were extrapolated to zero ionic strength by means of the Davies equation. For both U(VI) and Am(III), three consecutive acetate complexes with log(β

Molecular organization via ionic interactions at interfaces. 1. Monolayers and LB films of cyclic bisbipyridinium tetracations and dimyristoylphospha…

1993

Study of the effect of the membrane composition on ion transfer across a supported liquid membrane

2003

Abstract The rate of ion transfer across the supported liquid membrane (SLM) is studied in the rotating diffusion cell (RDC), varying the chemical composition of the SLM from net-cloth supported gel membranes to radiation-grafted polymer membranes. Steady-state current–voltage curves are measured as a function of the rotation rate, and values for the standard rate constant, k 0 , are determined for a series of tetraalkylammonium cations from the analysis of the initial slopes and the diffusion limiting currents. The analysis gives values for k 0 of the order of 10 −2 –10 −4 cm s −1 , which is in rather good agreement with the values found in the literature for this type of the system. As co…

Comparison of the performance of non-ionic and anionic surfactants as mobile phase additives in the RPLC analysis of basic drugs

2011

Surfactants added to the mobile phases in reversed-phase liquid chromatography (RPLC) give rise to a modified stationary phase, due to the adsorption of surfactant monomers. Depending on the surfactant nature (ionic or non-ionic), the coated stationary phase can exhibit a positive net charge, or just change its polarity remaining neutral. Also, micelles in the mobile phase introduce new sites for solute interaction. This affects the chromatographic behavior, especially in the case of basic compounds. Two surfactants of different nature, the non-ionic Brij-35 and the anionic sodium dodecyl sulfate (SDS) added to water or aqueous-organic mixtures, are here compared in the separation of basic …

Quantitative Retention−Structure and Retention−Activity Relationship Studies of Local Anesthetics by Micellar Liquid Chromatography

2011

The retention of compounds in micellar liquid chromatography (MLC) is governed by hydrophobic and electrostatic forces. For ionic compounds, both interactions should be considered. The present report offers a novel retention model that includes the hydrophobicity of compounds and the molar fraction of the charged form of compounds and compares it with other previously reported models. High correlations between the logarithm of capacity factors and these structural parameters were obtained for local anesthetics with different degrees of ionization using a nonionic surfactant solution as mobile phase. Modeling the retention of compounds as a function of physicochemical parameters and experime…