Electrostatic field polarization

A number of groups have criticized the ideas of Dauben and Noyce, especially the concept of PDC. Kamernitzsky and Akhrem, " in a thorough survey of the stereochemistry of addition reactions to carbonyl groups, accepted the existence of SAC but not of PDC. They point out that the reactions involve low energies of activation (10-13 kcal/mole) and suggest that differences in stereochemistry involve differences in entropies of activation. The effect favoring the equatorial alcohols is attributed to an electrostatic or polar factor (see also ref. 189) which may be determined by a difference in the electrostatic fields on the upper and lower sides of the carbonyl double bond, connected, for example, with the uncompensated dipole moments of the C—H bonds. The way this polar effect is supposed to influence the attack of the hydride is not made clear. 

Molecules do not consist of rigid arrays of point charges, and on application of an external electrostatic field the electrons and protons will rearrange themselves until the interaction energy is a minimum. In classical electrostatics, where we deal with macroscopic samples, the phenomenon is referred to as the induced polarization. I dealt with this in Chapter 15, when we discussed the Onsager model of solvation. The nuclei and the electrons will tend to move in opposite directions when a field is applied, and so the electric dipole moment will change. Again, in classical electrostatics we study the induced dipole moment per unit volume. 

The Electrical A nalogue of Magnetic Cooling. Three Processes bg Which Ions Are Introduced into Solution.. 1 Polar Dielectric in an Electrostatic Field. The Concepts of Faraday and Maxwell. The Electrostatic Energy in the Fields of Ions. The. Charging of a Condenser. The Amount of Free Energy Lost, by a Dielectric. The Behavior of Solvents in an Electrostatic Field. A Dielectric in the Field of a Charged Sphere. Two Types of Process Contrasted. 

Note 1. The Free Energy Lost by a Polar Dielectric in an Electrostatic Field. Let Fig. 76 depict a permanent rigid dipole whose axis makes an angle 0 with a uniform field of intensity E. If y is the dipole moment, the potential energy of the dipole in the field is — Ey cos 0. If the dipole is held in this fixed position, any increment dE in the intensity of the field will clearly mean a change in the potential energy of the dipole, equal to — y cos 0 dE. 

Electron-electron repulsion integrals, 28 Electrons bonding, 14, 18-19 electron-electron repulsion, 8 inner-shell core, 4 ionization energy of, 10 localization of, 16 polarization of, 75 Schroedinger equation for, 2 triplet spin states, 15-16 valence, core-valence separation, 4 wave functions of, 4,15-16 Electrostatic fields, of proteins, 122 Electrostatic interactions, 13, 87 in enzymatic reactions, 209-211,225-228 in lysozyme, 158-161,167-169 in metalloenzymes, 200-207 in proteins ... 

At any point r, the polarization P(r) and the total electrostatic field Etot(r) are assumed to be linearly related,... 

In order to quantify the importance of polarization effects in describing the electrostatic field of the system we compared this... 

As reviewed above, when a solute is placed in a dielectric medium, it electrically polarizes that medium. The polarized medium produces a local electrostatic field at the site of the solute, this field polarizes the solute, and the polarized solute interacts with the polarized medium. The interaction is typically too large to be treated by perturbation theory, and some sort of self-consistent treatment of polarized solute and polarized medium is more appropriate. At this point several options present themselves. It promotes orderly discussion to classify these... 

According to Hohenberg-Kohn theorem, 8p(F) given in Eq (36) does never vanishes because pA(r) and pY(r) are determined by different external potentials [26], Moreover, 8p(r) represents the electronic polarization contribution due to the isoelectronic change under the influence of the external electrostatic field. 

An electric field induces a dipole moment in non-polar solvent molecules and consequently these molecules become electrostatically aligned with the electric field according to the field polarity. Hence, the dielectric constant describes the capacity of a solvent to separate the electric charges of a solute through an appropriate orientation of its molecules. 

The classical CoMFA procedure relies on sterical and electrostatic fields or on spatial interaction energy maps of the potential ligands with standardized hydrophobic or polar probe molecules [56]. In this work, the modified ComPharm approach described in detail elsewhere [25] will be used. Its key differences with respect to classical CoMFA are the following ... 

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