scholarly journals Influence of Isotopologue Dipole Moments on Precision Dielectric-Constant Measurements

Author(s):  
Allan H. Harvey

Measurements of the relative permittivity (static dielectric constant) of fluids such as methane have been interpreted with the assumption of zero dipole moment. This assumption is not strictly true, due to the presence of isotopologues with small, nonzero dipole moments. We investigate the significance of this effect by analyzing the effect of the dipole of CH3D on the static dielectric constant of methane. It is found that the isotopologue effect is more than two orders of magnitude smaller than the uncertainty of the best existing measurements. Similar estimates for other compounds such as H2 and CO2 produce even smaller effects. Therefore, the interpretation of these measurements with a dipole moment of zero remains valid.

1975 ◽  
Vol 30 (3) ◽  
pp. 287-291 ◽  
Author(s):  
I. Gryczyński ◽  
A. Kawski

A variation of the temperature changes the static dielectric constant (ε) and the refractive index (n) of solvents and, in conjunction with the measurement of solvent shifts of absorption and fluorescence maxima, allows the investigation of dipole moment changes of solutes in the excited state. For this purpose, investigations of the temperature dependences of ε and n of some pure and mixed solvents of different polarities have been made. It is found that the excited dipole moments of indole, 1,2-dimethylindole, 2,3-dimethylindole and tryptophan obtained from the shifts of the fluorescence maxima in mixed solvents at high temperatures are in good agreement with those obtained in other ways.


1936 ◽  
Vol 9 (2) ◽  
pp. 296-300
Author(s):  
Shû Kambara

Abstract Natural rubber was purified by Pummerer's method and was dissolved in benzene and ether. The dielectric constant, refractive index, density, and concentration of the solutions were determined. From these data, the molecular polarization and dipole moment were calculated on the assumption that the rubber was dissolved in a molecular state of (C5H8)8. The dipole moments of total and gel rubber were found to be 2.45 and 2.91 × 10−18, respectively. These values are of the same order of magnitude as those of masticated crude rubber obtained by Ostwald. It may be said that the impurities of rubber are interlocked mechanically on the rubber molecule and are not combined chemically. Sol rubber in ether solution shows a far lower value than the values of total and gel rubber. These latter values may be influenced by autoöxidation, and the true value of the rubber hydrocarbon may be far smaller than the result described in this paper.


The infra-red absorption of ionic crystals differs in important details from the predictions of the theory based on first approximations. It is known that this discrepancy may be due to two effects which are neglected in such a theory, namely, to the anharmonic terms in the potential energy and to those terms in the dipole moment which are of higher order than the first in the displacement co-ordinates. These higher-order terms in the dipole moment arise from the deformation of the electron shells. The present paper develops in a systematic way the influence of these higher-order effects on the static dielectric constant. Because of the dispersion relations, the terms occurring in the static dielectric constant must also appear in the infra-red absorption spectrum . It is found that the third- and the fourth-order potential, the second- and the third-order dipole moment, and cross-terms between the second-order moment and the third-order potential, all con­tribute terms in the same order to the static dielectric constant. It is also found that the third-order potential contains important contributions from the long-range dipolar inter­action. These dipolar contributions are proportional to the product of the first- and second-order dipole moments, and it follows that in ionic crystals a large second-order moment automatically results in a large third-order potential. It is suggested that these dipolar contributions to the third-order potential may be responsible for the fact that in the infra-red spectra of different ionic crystals not only the intensity of the side band but also the width of the main band varies in the same way as the deformability of the electron shells.


1966 ◽  
Vol 21 (9) ◽  
pp. 1373-1376 ◽  
Author(s):  
A. Schweig ◽  
C. Reichardt

The ground state dipole moment of the π-electrons of 2.4.6-triphenyl-N- [3.5-di-tert-butyl-4-hydroxy-phenyl] -pyridinium-betain I, a highly solvatochromic substance, was determined by measuring the dielectric constant of a dilute solution and calculating first the dipole moment of the whole system (σ- and π-electrons) using the method of HALVERSTADT and KUMLER. The dipole moment of the π-electrons was then calculated, asuming the π-electron dipole to be imbedded in a spherical medium of dielectric constant 2. The value calculated by this method was compared with the π-electron dipole moment directly obtained from the dielectric constant of the dilute solution using a method of H. KUHN. This method is based on the assumption that a π-electron of a dissolved molecule sees the σ-electrons of the molecule and of the surrounding solvent, a saturated hydrocarbon, as a continuous uniform medium of dielectric constant 2. Thus the π-electron dipole of the solute molecule is regarded as being imbedded in a continuous medium of dielectric constant 2. It was found that the values of the π-electron dipole moments determined by the two methods agree well. Furthermore these experimental values agree with a theoretical value obtained in the case of N- [4-hydroxy-phenyl] -pyridinium-betain II using the one dimensional electron gas method including electron repulsion. The order of magnitude of the π-electron dipole moment of I clearly shows that the ground state of this molecule is highly polar.


2008 ◽  
Vol 73 (6-7) ◽  
pp. 873-897 ◽  
Author(s):  
Vladimír Špirko ◽  
Ota Bludský ◽  
Wolfgang P. Kraemer

The adiabatic three-dimensional potential energy surface and the corresponding dipole moment surface describing the ground electronic state of HN2+ (Χ1Σ+) are calculated at different levels of ab initio theory. The calculations cover the entire bound part of the potential up to its lowest dissociation channel including the isomerization barrier. Energies of all bound vibrational and low-lying ro-vibrational levels are determined in a fully variational procedure using the Suttcliffe-Tennyson Hamiltonian for triatomic molecules. They are in close agreement with the available experimental numbers. From the dipole moment function effective dipoles and transition moments are obtained for all the calculated vibrational and ro-vibrational states. Statistical tools such as the density of states or the nearest-neighbor level spacing distribution (NNSD) are applied to describe and analyse general patterns and characteristics of the energy and dipole results calculated for the massively large number of states of the strongly bound HN2+ ion and its deuterated isotopomer.


RSC Advances ◽  
2021 ◽  
Vol 11 (9) ◽  
pp. 5179-5181
Author(s):  
Sayantan Mondal ◽  
Biman Bagchi

Neglects of inherent anisotropy and distinct dielectric boundaries may lead to completely erroneous results. We demonstrate that such mistakes can give rise to gross underestimation of the static dielectric constant of cylindrically nanoconfined water.


2013 ◽  
Vol 28 (29) ◽  
pp. 1350147 ◽  
Author(s):  
TAKESHI FUKUYAMA ◽  
ALEXANDER J. SILENKO

General classical equation of spin motion is explicitly derived for a particle with magnetic and electric dipole moments in electromagnetic fields. Equation describing the spin motion relative to the momentum direction in storage rings is also obtained.


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