Electric field external

The interaction of an electronic charge distribution p(r) with an electric potential /(r) gives an energy correction. 

Since the electric field (F = —dV/dr) normally is fairly uniform at the molecular level, it is useful to write as a multipole expansion. 

Here q is the net charge (monopole), p, is the (electric) dipole moment, Q is the quadrupole moment, and F and F are the field and field gradient d /dr), respectively. The dipole moment and electric field are vectors, and the pF term should be interpreted as the dot product (p F = + EyPy + Ez z)- I e quadrupole moment and field 

In the absence of an external field, the unperturbed dipole and quadrupole moments may be calculated from the electronic wave function as simple expectation values. 

The superscript t denotes a transposition of the r-vector, i.e. converting it from a column to a row vector. The rr notation for the quadmpole moment therefore indicates a 3 x 3 matrix containing the products of the x-, y- and z-coordinates, e.g. the Qxy component is calculated as the expectation value of xy. 

The presence of a field influences the wave function, and leads to induced dipole, quadrupole etc. moments. For the dipole moment this may be written as--------------------- 

Since the electric field (F = is normally fairly uniform at the molecular level, 

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Assuming that the system has no pennanent dipole moment, tire existence ofP(t) depends on a non-stationary j induced by an external electric field. For weak fields, we may expand the polarization in orders of the perturbation. 

In addition, there could be a mechanical or electromagnetic interaction of a system with an external entity which may do work on an otherwise isolated system. Such a contact with a work source can be represented by the Hamiltonian U p, q, x) where x is the coordinate (for example, the position of a piston in a box containing a gas, or the magnetic moment if an external magnetic field is present, or the electric dipole moment in the presence of an external electric field) describing the interaction between the system and the external work source. Then the force, canonically conjugate to x, which the system exerts on the outside world is... 

Migration is the movement of ions due to a potential gradient. In an electrochemical cell the external electric field at the electrode/solution interface due to the drop in electrical potential between the two phases exerts an electrostatic force on the charged species present in the interfacial region, thus inducing movement of ions to or from the electrode. The magnitude is proportional to the concentration of the ion, the electric field and the ionic mobility. 

When ions move under equilibrium conditions in a gas and an external electric field, the energy gained from the electric field E between collisions is lost to the gas upon collision so that the ions move with a constant drift speed v = KE. The mobility K of ions of charge e in a gas of density N is given in tenns of the collision integral by the Chapman-Enskog fomuila [2]... 

The application of a small external electric field A to a semiconductor results in a net average velocity component of the carriers (electrons or holes) called the drift velocity, v. The coefficient of proportionality between E and is known as the carrier mobility p. At higher fields, where the drift velocity becomes comparable to the thennal... 

Our discussion of elecfronic effects has concentrated so far on permanent features of the cliarge distribution. Electrostatic interactions also arise from changes in the charge distribution of a molecule or atom caused by an external field, a process called polarisation. The primary effect of the external electric field (which in our case will be caused by neighbouring molecules) is to induce a dipole in the molecule. The magnitude of the induced dipole moment ginj is proportional to the electric field E, with the constant of proportionahty being the polarisability a ... 

The perturbation V = H-H appropriate to the particular property is identified. For dipole moments ( i), polarizabilities (a), and hyperpolarizabilities (P), V is the interaction of the nuclei and electrons with the external electric field... 

The most important materials among nonlinear dielectrics are ferroelectrics which can exhibit a spontaneous polarization PI in the absence of an external electric field and which can spHt into spontaneously polarized regions known as domains (5). It is evident that in the ferroelectric the domain states differ in orientation of spontaneous electric polarization, which are in equiUbrium thermodynamically, and that the ferroelectric character is estabUshed when one domain state can be transformed to another by a suitably directed external electric field (6). It is the reorientabiUty of the domain state polarizations that distinguishes ferroelectrics as a subgroup of materials from the 10-polar-point symmetry group of pyroelectric crystals (7—9). 

Ions of an electrolyte are free to move about in solution by Brownian motion and, depending on the charge, have specific direction of motion under the influence of an external electric field. The movement of the ions under the influence of an electric field is responsible for the current flow through the electrolyte. The velocity of migration of an ion is given by ... 

Formal Theory A small neutral particle at equihbrium in a static elecdric field experiences a net force due to DEP that can be written as F = (p V)E, where p is the dipole moment vecdor and E is the external electric field. If the particle is a simple dielectric and is isotropically, linearly, and homogeneously polarizable, then the dipole moment can be written as p = ai E, where a is the (scalar) polarizability, V is the volume of the particle, and E is the external field. The force can then be written as ... 

Figure 6.1. (a) Atom not subject to external electric field. Centre of electron cloud and nucleus coincident, (b) Electron cloud displacement through application of external electric field, (c) Charged condenser plates separated by vacuum, (d) Condenser plates separated by dielectric... 

According to the field charging theory, the external electric field drives ions to the aerosol particle until the repelling electric field prevents ions from reaching the surface of the particle. This condition corresponds to the saturation i.e, the particle has reached a stable value which cannot be exceeded. The relationship between the net charge of the particle and charging time is given by... 

According to Eq. (13.52), saturation charge is directly proportional to the square of the particle diameter and the external electric field. Particle charging depends also on the composition of the particle, which is taken into account by the relative dielectric constant e,. It is worth noticing that the field charging model should not be applied for small particles (dp < 0.5 pm). 

The molecular simulations also showed that electro-osmosis is also observed in aqueous electrolyte solutions, as long as the external electric field is reversed periodically to prevent the ions from accumulating near the membrane. An example of this is shown in Fig. 10, which shows the effect of an electric field on a 4.67 mole percent aqueous LiCl solution at 25°C. It is quite clear that the mobility of the solvent molecules increases as a result of... 

Carbon atoms in free space have spherical symmetry, but a carbon atom in a molecule is a quite different entity because its charge density may well distort from spherical symmetry. To take account of the finer points of this distortion, we very often need to include d, f,. .. atomic orbitals in the basis set. Such atomic orbitals are referred to as polarization functions because their inclusion would allow a free atom to take account of the polarization induced by an external electric field or by molecule formation. 1 mentioned polarization functions briefly in Section 9.3.1. 

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