Dielectric constant vacuum

T. Simonson. Accurate calculation of the dielectric constant of water from simulations of a microscopic droplet in vacuum. Chem. Phys. Lett, 250 450-454, 1996. 

By using an effective, distance-dependent dielectric constant, the ability of bulk water to reduce electrostatic interactions can be mimicked without the presence of explicit solvent molecules. One disadvantage of aU vacuum simulations, corrected for shielding effects or not, is the fact that they cannot account for the ability of water molecules to form hydrogen bonds with charged and polar surface residues of a protein. As a result, adjacent polar side chains interact with each other and not with the solvent, thus introducing additional errors. 

The angles ot, p, and x relate to the orientation of the dipole nionient vectors. The geonieti y of interaction between two bonds is given in Fig. 4-16, where r is the distance between the centers of the bonds. It is noteworthy that only the bond moments need be read in for the calculation because all geometr ic features (angles, etc.) can be calculated from the atomic coordinates. A default value of 1.0 for dielectric constant of the medium would normally be expected for calculating str uctures of isolated molecules in a vacuum, but the actual default value has been increased 1.5 to account for some intramolecular dipole moment interaction. A dielectric constant other than the default value can be entered for calculations in which the presence of solvent molecules is assumed, but it is not a simple matter to know what the effective dipole moment of the solvent molecules actually is in the immediate vicinity of the solute molecule. It is probably wrong to assume that the effective dipole moment is the same as it is in the bulk pure solvent. The molecular dipole moment (File 4-3) is the vector sum of the individual dipole moments within the molecule. 

The dielectric constant is a property of a bulk material, not an individual molecule. It arises from the polarity of molecules (static dipole moment), and the polarizability and orientation of molecules in the bulk medium. Often, it is the relative permitivity 8, that is computed rather than the dielectric constant k, which is the constant of proportionality between the vacuum permitivity so and the relative permitivity. 

Solvent Effects on the Rate of Substitution by the S l Mechanism Table 8 6 lists the relative rate of solvolysis of tert butyl chloride m several media m order of increasing dielectric constant (e) Dielectric constant is a measure of the ability of a material m this case the solvent to moderate the force of attraction between oppositely charged par tides compared with that of a standard The standard dielectric is a vacuum which is assigned a value e of exactly 1 The higher the dielectric constant e the better the medium is able to support separated positively and negatively charged species 8olvents... 

The dielectric constant (permittivity) tabulated is the relative dielectric constant, which is the ratio of the actual electric displacement to the electric field strength when an external field is applied to the substance, which is the ratio of the actual dielectric constant to the dielectric constant of a vacuum. The table gives the static dielectric constant e, measured in static fields or at relatively low frequencies where no relaxation effects occur. 

Dielectric Constant. Dielectric constant or specific inductive capacity (SIC) is both defined and measured by the ratio of the electric capacity of a condenser having that material as the dielectric to the capacity of the same condenser having air as the dielectric. The dielectric constant of vacuum is unity. Dry air has a constant slightly higher but for most practical purposes it is considered as unity. 

C = Q/V. In a vacuum, the charge density on the surfaces of the conductors is affected by the permittivity of free space, q. When a dielectric material is placed between the conductors, the capacitance increases because of the higher permittivity, e, of the material. The ratio of e and q gives the dielectric constant, K, of the material, k = e/eg The dielectric constant of siHca glass is 3.8. 

Dielectric Constant The dielectric constant of material represents its ability to reduce the electric force between two charges separated in space. This propei ty is useful in process control for polymers, ceramic materials, and semiconduc tors. Dielectric constants are measured with respect to vacuum (1.0) typical values range from 2 (benzene) to 33 (methanol) to 80 (water). TEe value for water is higher than for most plastics. A measuring cell is made of glass or some other insulating material and is usually doughnut-shaped, with the cylinders coated with metal, which constitute the plates of the capacitor. 

As for the dielectric constant, when explicit solvent molecules are included in the calculations, a value of 1, as in vacuum, should be used because the solvent molecules themselves will perform the charge screening. The omission of explicit solvent molecules can be partially accounted for by the use of an / -dependent dielectric, where the dielectric constant increases as the distance between the atoms, increases (e.g., at a separation of 1 A the dielectric constant equals 1 at a 3 A separation the dielectric equals 3 and so on). Alternatives include sigmoidal dielectrics [80] however, their use has not been widespread. In any case, it is important that the dielectric constant used for a computation correspond to that for which the force field being used was designed use of alternative dielectric constants will lead to improper weighting of the different electrostatic interactions, which may lead to significant errors in the computations. 

The influence of a particular dielectric on the capacitance of a condenser is conveniently assessed by the dielectric constant, also known as the relative permittivity or rarely specific inductive capacity. This is defined as the ratio of the relative condenser capacity, using the given material as a dielectric, to the capacity of the same condenser, without dielectric, in a vacuum (or for all practical intents and purposes, air). 

Figures 17A and 17B (p. 183) show energy as a function of rotation for a series of 1-substituted acetaldehydes, with 6 = 0° in the syn conformation and 6 = 180° in the anti conformation. The calculations were done using the PM3 method. Figure 17A for a vacuum, whereas Fig. 17B is for a solvent cavity with a dielectric constant of 4." The table gives the calculated barriers. Discuss the following aspects (a) rationalize the order Br > Cl > F for syn conformers (b) rationalize the shift to favor the am. conformation in the more polar environment. 

It should be noted that, if the medium between the particle and substrate is something other than vacuum and possesses a dielectric constant e, the interaction energy in Eq. 68 is reduced by a factor of Eq. 68, which relates the interaction energy between permanent electric dipoles and their separation distances is known as the Keesom effect. 

The insulating property of any insulator will break down in a sufficiently strong electric field. The dielectric strength is defined as the electric strength (V/m) which an insulating material can withstand. For plastics the dielectric strength can vary from 1 to 1000 MV/m. Materials may be compared on the basis of their relative permittivity (or dielectric constant). This is the ratio of the permittivity of the material to the permittivity of a vacuum. The ability of a... 

Table 8-2 lists several physical properties pertinent to our concern with the effects of solvents on rates for 40 common solvents. The dielectric constant e is a measure of the ability of the solvent to separate charges it is defined as the ratio of the electric permittivity of the solvent to the permittivity of the vacuum. (Because physicists use the symbol e for permittivity, some authors use D for dielectric constant.) Evidently e is dimensionless. The dielectric constant is the property most often associated with the polarity of a solvent in Table 8-2 the solvents are listed in order of increasing dielectric constant, and it is evident that, with a few exceptions, this ranking accords fairly well with chemical intuition. The dielectric constant is a bulk property. 

If we now transfer our two interacting particles from the vacuum (whose dielectric constant is unity by definition) to a hypothetical continuous isotropic medium of dielectric constant e > 1, the electrostatic attractive forces will be attenuated because of the medium s capability of separating charge. Quantitative theories of this effect tend to be approximate, in part because the medium is not a structureless continuum and also because the bulk dielectric constant may be an inappropriate measure on the molecular scale. Eurther discussion of the influence of dielectric constant is given in Section 8.3. 

The simplest reaction field model is a spherical cavity, where only the net charge and dipole moment of the molecule are taken into account, and cavity/dispersion effects are neglected. For a net charge in a cavity of radius a, the difference in energy between vacuum and a medium with a dielectric constant of e is given by the Bom model. ... 

Capacitance is related to the area of the plates (yi), the distance between the plates (d), and the dielectric constant (e) of the material between the plates (Figure 2, equation I). The dielectric constant or permittivity of a material is the increased capacitance observed compared to the condition if a vacuum was present between the plates. Common dielectric materials are polystyrene (e = 2.5), mylar (e = 3), mica (e = 6), aluminum oxide (e = 7), tantalum oxide (e = 25), and titania (e = 100). In the Leyden jar the dielectric is silica. 

The Amount of Free Energy Lost by a Dielectric. The above considerations apply to fields of any intensity. When we are dealing only with ordinary weak fields, for which the polarization is proportional to the field (the straight part of the curve in Fig. 5), the substance under discussion is said to possess a dielectric constant. This will be denoted by t. In a vacuum e is set equal to unity and in a dielectric the polarization is proportional to (t — 1). The loss of free energy by the dielectric may be expressed in terms of e. In Note 1 of the Appendix at the end of this book it is shown that, when a homogeneous slab is introduced into a uniform field of initial intensity X, the free energy lost per unit volume amounts to... 

Let us now consider the same species of molecule situated in a particular solvent and dissociated into a pair of ions. The potential-energy curve will be similar but will have a much shallower minimum, as in Fig. 86, because in a medium of high dielectric constant the electrostatic attraction is much weaker. Let the dissociation energy in solution be denoted by D, in contrast to the larger Dvac, the value in a vacuum. 

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