Electric Polarization of Onsager Fluids. II. Birefringence. 2. Molar Kerr Constants of Binary Solutions

Electric polarization of Onsager fluids

The problem of correct determination of electrical and optical characteristics of molecules of dielectric fluids can actually be brought to problem of description of the effective internal field which consist of the field included by external sources and the cumulate electric field of molecules on the medium including intermolecular interactions. An attempt was made to modify the model Onsager theory. A polarizable molecular dipole enclosed in spherical cavity is substituted for a rigid one submerged in polarizable medium which fills the cavity. The local dielectric permittivity of the Heaviside type is replaced for the oscillating, rapidly damping function of Fresnel integral. The analytic…

Intermolecular coupling influence on conformations of molecules in solution

Abstract The influence of non-specific intermolecular interactions on conformational equilibria of organic molecules is investigated with the help of the London-Debye-Keesom pair coupling potentials. It is shown that in a series of apolar solvents equilibrium constant logarithms are proportional to ζα ≡ Z αs/ R 6s,d, and in a series of polar solvents equilibrium constants logarithms are proportional to ζμ ≡ Z μ2s/ R 6s,d, where Z is the average number of neighbours of a solute molecule in the first coordination sphere, αs is the polarizability, μs the dipole moment of solvent molecules, and R s,d = R s + R d is the sum of the radii of spherical volumes per molecule of solvent (s) and dissol…

Molecular structure and electric properties of N -methyl- N -nitroaniline and its derivatives

A comparative study of the molecular structure of N-methyl-N-nitroaniline and its derivatives is carried out employing the Kerr effect and dipole moments methods in combination with the crystallographic analysis. The obtained experimental structural data agree with the quantum-chemical calculations by the B3LYP/6-31G p and MP2/3-21G p methods. The measurement and calculation results are used to draw conclusions about the mutual interaction and role of various substituents to the Nmethyl-N-nitroaniline molecule. q 2001 Elsevier Science B.V. All rights reserved.

Studies on the proton acceptor ability of phosphoryl compounds

Abstract Dipole moments and molar Kerr constants of complexes of phenols with phosphoryl compounds were studied to establish the structure of complexes and parameters characterizing the proton acceptor ability of these compounds. The structures of these complexes and parameters ( μ H , Δ ( mk ) S , log K and δ 0 ) were established. It has been suggested that a new parameter Δ ( mK ) S — structural additive difference of the molar Kerr constant — makes it possible to determine changes of polarity and polarizability of the systems during complex formation.

Studies on proton acceptor ability of SOx-containing compounds

Abstract IR spectra, dipole moments and molar Kerr constants of complexes of phenols with compounds containing SO x groups were studied to establish the structure of the complexes and the parameters characterizing the proton acceptor capability of these compounds. ( μ H , Δ ( mK ), log K and δ 0 ). It has been suggested that the new parameter Δ ( mK ) — the structural additive difference of the molar Kerr constant — makes it possible to determine changes of polarity and polarizability of the systems during complex formation.