Effects in dipole

Matyushov, D.V., Ladanyi, B.M. Nonlinear effects in dipole solvation. II. Optical spectra and electron transfer activation, J. Chem. Phys. 107, 1375—1387 (1997)... 

A pioneer effort to the account for electrostatic interaction effects in dipole reorientations and correlation functions was made by Brot and Darmon (39) in their Monte Carlo simulations for the partially ordered solid phase of 1 2 3 trichloro 4 5 6 trimethyl benzene (TCTMB) using the point charge model already mentioned in 2.4. Calculations of transition rates between 6 fold rotational wells of fluctuating depth as a result of changing neighbor orientations resulted in essentially Debye relaxation at 300 Kt but a second simulation at 186 K for which considerable rotational ordering is present produced very nearly a circular arc with od = 0.28 as compared to the experimental Ad = 0.39. 

Bailey C G, Dessent C E FI, Johnson M A and Bowen K FI 1996 Vibronic effects in the photon energy-dependent photoelectron spectra of the CFIjCN dipole-bound anion J. Chem. Phys. 104 6976-83... 

In order to illustrate some of the basic aspects of the nonlinear optical response of materials, we first discuss the anliannonic oscillator model. This treatment may be viewed as the extension of the classical Lorentz model of the response of an atom or molecule to include nonlinear effects. In such models, the medium is treated as a collection of electrons bound about ion cores. Under the influence of the electric field associated with an optical wave, the ion cores move in the direction of the applied field, while the electrons are displaced in the opposite direction. These motions induce an oscillating dipole moment, which then couples back to the radiation fields. Since the ions are significantly more massive than the electrons, their motion is of secondary importance for optical frequencies and is neglected. 

Several structural factors have been considered as possible causes of the anomeric effect. In localized valence bond terminology, it can be recognized that there will be a dipole-dipole repulsion between the polar bonds at the anomeric carbon in the equatorial conformation. This dipole-dipole interaction is reduced in the axial conformation, and this factor probably contributes to the solvent dependence of the anomeric effect. 

When iodine chloride is heated to 27°C, the weak intermolecular forces are unable to keep the molecules rigidly aligned, and the solid melts. Dipole forces are still important in the liquid state, because the polar molecules remain close to one another. Only in the gas, where the molecules are far apart, do the effects of dipole forces become negligible. Hence boiling points as well as melting points of polar compounds such as Id are somewhat higher than those of nonpolar substances of comparable molar mass. This effect is shown in Table 9.3. 

In molecular doped polymers the variance of the disorder potential that follows from a plot of In p versus T 2 is typically 0.1 eV, comprising contributions from the interaction of a charge carrier with induced as well as with permanent dipoles [64-66]. In molecules that suffer a major structural relaxation after removal or addition of an electron, the polaron contribution to the activation energy has to be taken into account in addition to the (temperature-dependent) disorder effect. In the weak-field limit it gives rise to an extra Boltzmann factor in the expression for p(T). More generally, Marcus-type rates may have to be invoked for the elementary jump process [67]. 

Dielectric loss The dielectric loss factor represents energy that is lost to the insulator as a result of its being subjected to alternating current (AC) fields. The effect is caused by the rotation of dipoles in the plastic structure and by the displacement effects in the plastic chain caused by the electrical fields. The frictional effects cause energy absorption and the effect is analogous to the mechanical hysteresis effects except that the motion of the material is field induced instead of mechanically induced. 

Of the five sets which were correlated with eq. (2), four gave significant correlations. Values of Pr are in the range 50 to 54, which indicates approximately equal contributions of the localized and delocalized effects. Thus, dipole moments of substituted acetylenes could be correlated successfully with the Up constants. 

The racemization of the phosphine (118) has been followed by optical rotation. The lack of a solvent effect indicates that there is little change in dipole moment in the formation of the planar transition state. Circular dichroism has been used to study the interactions of nucleotides with proteins and DNA with a histone. Faraday effects have been reviewed. Refraction studies on chloro-amino-phosphines, fluoro-amino-phosphines, and some chalcogenides are reported. 

The dipole moment of tributylpliosphine varies from 1.49 to 2.4 D according to the solvent used. Inductive effects in phosphines have been estimated by comparing the calculated and observed dipole moments, and the apparent dipole moment due to the lone electron pair on phosphorus has been estimated. A method of calculating the hybridization of the phosphorus atom in terms of bond angles is suggested which leads to a linear relationship between hybridization ratio and lone electron pair moment. The difference between experimental and calculated dipole moments for para-substitued arylphosphines, phosphine sulphides, and phosphinimines has been used to estimate mesomeric transfer of electrons to phosphorus. 

Schwerdtfeger, P. and Bowmaker, G.A. (1994) Relativistic effects in gold chemistry. V. Group 11 Dipole-Polarizabilities and Weak Bonding in Monocarbonyl Compounds. Journal of Chemical Physics, 100, 4487-4497. 

Fig. 4.9 Magnetic dipole splitting (nuclear Zeeman effect) in pe and resultant Mossbauer spectrum (schematic). The mean energy of the nuclear states is shifted by the electric monopole interaction which gives rise to the isomer shift 5. Afi. g = Sg/tN and A M,e = refer to the...

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