Solvent electric field

Interactions between a solute and a solvent may be broadly divided into three types specific interactions, reaction field and Stark effects, and London-van-der-Waals or dispersion interactions. Specific interactions involve such phenomena as ion pair formation, hydrogen bonding and ir-complexing. Reaction field effects involve the polarization of the surrounding nonpolar solvent by a polar solute molecule resulting in a solvent electric field at the solute molecule. Stark effects involve the polarization of a non-polar solute by polar solvent molecules Dispersion interactions, generally the weakest of the three types, involves nonpolar solutes and nonpolar solvents via snap-shot dipole interactions, etc. For our purposes it is necessary to develop both the qualitative and semiquantita-tive forms in which these kinds of interactions are encountered in studies of solvent effects on coupling constants. 

The qualitative example presented above describes the isolated formaldehyde molecule. In solution the large permanent dipole moment or hydrogen bonding of formaldehyde will induce an appreciable solvent electric field whose orientation in the molecular coordinate system is fixed (presumably parallel to... 

In Eq. (1-6), E) , vcnt refers to the total solvent electric field and it contains a sum of contributions from the point charges and the induced dipole moments in the MM part of the system. Such a field (and hence the induced dipole) depends on all other induced dipole moments in the solvent. This means that Eq. (1-6) must be solved iteratively within each SCF iteration. As an alternative, Eq. (1-6) may be reformulated into a matrix equation... 

Kjaer el al. have performed a benchmark study of a combined multipole spin-spin coupling constant polarizability/reaction field (MJP/RF) approach to the calculation of both specific and bulk solvation effects on coupling in solvated molecule. The MJP/RF approach was based on the expansion of couplings of the solvated molecule in terms of coupling dipole and quadrupole polarizabilities and hyperpolarizabilities derived from single ab initio calculations, and on taking into account solvent electric field and electric field gradient calculated by molecular dynamics (MD)... 

Figure 3 Evolution of the solvent electric field E.(t) along the 0-0 vector calculated at the middle point between both oxygens along the 6 ps simulation (from Ref 30)...

H. R (1996) Evidence by NMR of temperature-dependent solvent electric field effects on proton transfer and hydrogen bond geometries. Z. Phys. Chem., 196, 73-84. 

As described at the end of section Al.6.1. in nonlinear spectroscopy a polarization is created in the material which depends in a nonlinear way on the strength of the electric field. As we shall now see, the microscopic description of this nonlinear polarization involves multiple interactions of the material with the electric field. The multiple interactions in principle contain infomiation on both the ground electronic state and excited electronic state dynamics, and for a molecule in the presence of solvent, infomiation on the molecule-solvent interactions. Excellent general introductions to nonlinear spectroscopy may be found in [35, 36 and 37]. Raman spectroscopy, described at the end of the previous section, is also a nonlinear spectroscopy, in the sense that it involves more than one interaction of light with the material, but it is a pathological example since the second interaction is tlirough spontaneous emission and therefore not proportional to a driving field... 

It is important to recognize the approximations made here the electric field is supposed to be sulficiently small so that the equilibrium distribution of velocities of the ions is essentially undisturbed. We are also assuming that the we can use the relaxation approximation, and that the relaxation time r is independent of the ionic concentration and velocity. We shall see below that these approximations break down at higher ionic concentrations a primary reason for this is that ion-ion interactions begin to affect both x and F, as we shall see in more detail below. However, in very dilute solutions, the ion scattering will be dominated by solvent molecules, and in this limiting region A2.4.31 will be an adequate description. 

The electronic transitions which produce spectra in the visible and ultraviolet are accompanied by vibrational and rotational transitions. In the condensed state, however, rotation is hindered by solvent molecules, and stray electrical fields affect the vibrational frequencies. For these reasons, electronic bands are very broad. An electronic band is characterised by the wave length and moleculai extinction coefficient at the position of maximum intensity (Xma,. and emai.). 

Electroosmotic Mobility When an electric field is applied to a capillary filled with an aqueous buffer, we expect the buffer s ions to migrate in response to their electrophoretic mobility. Because the solvent, H2O, is neutral, we might reasonably expect it to remain stationary. What is observed under normal conditions, however, is that the buffer solution moves toward the cathode. This phenomenon is called the electroosmotic flow. 

Other perturbations have been demonstrated. The pressure,, jump, similar to the T-jump in principle, is attractive for organic reactions where Joule heating may be impractical both because of the solvent being used and because concentrations might have to be measured by conductivity. Large (10 —10 kPa) pressures are needed to perturb equiUbrium constants. One approach involves pressurizing a Hquid solution until a membrane mptures and drops the pressure to ambient. Electric field perturbations affect some reactions and have also been used (2), but infrequentiy. 

Disadvantages associated with some organic solvents include toxicity flammabiHty and explosion ha2ards sensitivity to moisture uptake, possibly leading to subsequent undesirable reactions with solutes low electrical conductivity relatively high cost and limited solubiHty of many solutes. In addition, the electrolyte system can degrade under the influence of an electric field, yielding undesirable materials such as polymers, chars, and products that interfere with deposition of the metal or alloy. 

A parameter used to characterize ER fluids is the Mason number, Af, which describes the ratio of viscous to electrical forces, and is given by equation 14, where S is the solvent dielectric constant T q, the solvent viscosity 7, the strain or shear rate P, the effective polarizabiUty of the particles and E, the electric field (117). 

A finite time is required to reestabUsh the ion atmosphere at any new location. Thus the ion atmosphere produces a drag on the ions in motion and restricts their freedom of movement. This is termed a relaxation effect. When a negative ion moves under the influence of an electric field, it travels against the flow of positive ions and solvent moving in the opposite direction. This is termed an electrophoretic effect. The Debye-Huckel theory combines both effects to calculate the behavior of electrolytes. The theory predicts the behavior of dilute (<0.05 molal) solutions but does not portray accurately the behavior of concentrated solutions found in practical batteries. 

Electrically assisted transdermal dmg deflvery, ie, electrotransport or iontophoresis, involves the three key transport processes of passive diffusion, electromigration, and electro osmosis. In passive diffusion, which plays a relatively small role in the transport of ionic compounds, the permeation rate of a compound is deterrnined by its diffusion coefficient and the concentration gradient. Electromigration is the transport of electrically charged ions in an electrical field, that is, the movement of anions and cations toward the anode and cathode, respectively. Electro osmosis is the volume flow of solvent through an electrically charged membrane or tissue in the presence of an appHed electrical field. As the solvent moves, it carries dissolved solutes. 

The continuum electrostatic approximation is based on the assumption that the solvent polarization density of the solvent at a position r in space is linearly related to the total local electric field at that position. The Poisson equation for macroscopic continuum media... 

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