Polarizability field

A (h,x,s)> AE(h,x,0) and A (o,s) can be analyzed in terms of the Taft-Topsom formalism88 wherein these effects are decomposed into electronegativity, polarizability, field and resonance contributions, respectively measured by the descriptors ax, aa, Linear combinations of ax and or lead to a reasonably good description of the AE values indicated above. The main semiquantitative conclusions of such an analysis are as follows ... 

Bradley, M. and Waller, C.L. (2001) Polarizability fields for use in three-dimensional quantitative structure-activity relationship (3D-QSAR). 

A number of early studies also found good linear relationships between the pK s of alcohols and the sum of their Hammett or Taft substituent constants, o or o [191,277,278]. Takahashi et al. found that the pK s of a large collection of alcohols could be estimated using either Taft substituent constants or the carbonyl frequencies of their esters [265]. Taft and co-workers [193] found a strong relationship (r = 0.999) between the gas-phase pKj,s ol a collection of OH acids and empirical substituent constants representing polarizability, field-inductive, and resonance effects. These workers also... 

The acidities of substituted pyridines have been studied by a number of groups using several different methods. In 1951 Gero and Markham [371] found a linear relationship between the pK s of methyl pyridines and the number of methyl substituents. Abboud et al. [372] analyzed the gas-phase and aqueous acidities of a large number of substituted pyridines in terms of polarizability, field, and resonance contributions from the substituents. Chen and MacKerell [353] used AMI and MP2 calculations to examine substituent effects on pyridine pKj,s, concluding that the greatest shortcomings in the calculations stemmed from limitations of the solvent model. 

The energy of a polarizable atom 1 in a field E is again given by Eq. VI-10,... 

The charge redistribution that occurs when a molecule is exposed to an electric field is characterized by a set of constants called polarizabilities. In a imifonn electric field F, a component of the dipole moment is... 

The dipole polarizability tensor characterizes the lowest-order dipole moment induced by a unifonu field. The a tensor is syimnetric and has no more than six independent components, less if tire molecule has some synnnetry. The scalar or mean dipole polarizability... 

In linear, spherical and synnnetric tops the components of a along and perpendicular to the principal axis of synnnetry are often denoted by a and respectively. In such cases, the anisotropy is simply Aa = tty -If the applied field is oscillating at a frequency w, then the dipole polarizability is frequency dependent as well a(co). The zero frequency limit of the dynamic polarizability a(oi) is the static polarizability described above. 

There are higher multipole polarizabilities tiiat describe higher-order multipole moments induced by non-imifonn fields. For example, the quadnipole polarizability is a fourth-rank tensor C that characterizes the lowest-order quadnipole moment induced by an applied field gradient. There are also mixed polarizabilities such as the third-rank dipole-quadnipole polarizability tensor A that describes the lowest-order response of the dipole moment to a field gradient and of the quadnipole moment to a dipolar field. All polarizabilities of order higher tlian dipole depend on the choice of origin. Experimental values are basically restricted to the dipole polarizability and hyperpolarizability [21, 24 and 21]. Ab initio calculations are an imponant source of both dipole and higher polarizabilities [20] some recent examples include [26, 22] ... 

Consider the interaction of a neutral, dipolar molecule A with a neutral, S-state atom B. There are no electrostatic interactions because all the miiltipole moments of the atom are zero. However, the electric field of A distorts the charge distribution of B and induces miiltipole moments in B. The leading induction tenn is the interaction between the pennanent dipole moment of A and the dipole moment induced in B. The latter can be expressed in tenns of the polarizability of B, see equation (Al.S.g). and the dipole-mduced-dipole interaction is given by... 

Raman scattering has been discussed by many authors. As in the case of IR vibrational spectroscopy, the interaction is between the electromagnetic field and a dipole moment, however in this case the dipole moment is induced by the field itself The induced dipole is pj j = a E, where a is the polarizability. It can be expressed in a Taylor series expansion in coordinate isplacement... 

Flere, is the static polarizability, a is the change in polarizability as a fiinction of the vibrational coordinate, a" is the second derivative of the polarizability with respect to vibration and so on. As is usually the case, it is possible to truncate this series after the second tenn. As before, the electric field is = EQCOslnvQt, where Vq is the frequency of the light field. Thus we have... 

Between any two atoms or molecules, van der Waals (or dispersion) forces act because of interactions between the fluctuating electromagnetic fields resulting from their polarizabilities (see section Al. 5, and, for instance. 

The high-field output of laser devices allows for a wide variety of nonlinear interactions [17] between tire radiation field and tire matter. Many of tire initial relationships can be derived using engineering principles by simply expanding tire media polarizability in a Taylor series in powers of tire electric field ... 

Conformational Adjustments The conformations of protein and ligand in the free state may differ from those in the complex. The conformation in the complex may be different from the most stable conformation in solution, and/or a broader range of conformations may be sampled in solution than in the complex. In the former case, the required adjustment raises the energy, in the latter it lowers the entropy in either case this effect favors the dissociated state (although exceptional instances in which the flexibility increases as a result of complex formation seem possible). With current models based on two-body potentials (but not with force fields based on polarizable atoms, currently under development), separate intra-molecular energies of protein and ligand in the complex are, in fact, definable. However, it is impossible to assign separate entropies to the two parts of the complex. 

Equation (18) is valid when the polarizability of the dielectric is proportional to the electrostatic field strength [4]. The operator V in the Cartesian coordinate system has the form V = dldx,dldy,dldz). 

In Section 7.1.2 a method for the calculation of mean molecular polarizability was presented. Mean molecular polarizability can be calculated from additive contributions of the atoms in their various hybridization states in a molecule (see Eq. (6)). Mean molecular polarizability, a, expresses the magnitude of the dipole moment, fi, induced into a molecule imder the influence of an external field, E (Eq. (15))... 

Electrostatic terms other than the simple charge interactions above are commonly included in molecular mechanics calculations. particularly dipole-dipole interactions. More recently, second-order electrostatic interactions like those describing polarizability have been added to some force fields. 

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... 

Polarization is usually accounted for by computing the interaction between induced dipoles. The induced dipole is computed by multiplying the atomic polarizability by the electric field present at that nucleus. The electric field used is often only that due to the charges of the other region of the system. In a few calculations, the MM charges have been included in the orbital-based calculation itself as an interaction with point charges. 

The molecular quantities can be best understood as a Taylor series expansion. For example, the energy of the molecule E would be the sum of the energy without an electric field present, Eq, and corrections for the dipole, polarizability, hyperpolarizability, and the like ... 

Ah initio calculations of polymer properties are either simulations of oligomers or band-structure calculations. Properties often computed with ah initio methods are conformational energies, polarizability, hyperpolarizability, optical properties, dielectric properties, and charge distributions. Ah initio calculations are also used as a spot check to verify the accuracy of molecular mechanics methods for the polymer of interest. Such calculations are used to parameterize molecular mechanics force fields when existing methods are insulficient, which does not happen too often. 

Polarizability (Section 4 6) A measure of the ease of distortion of the electric field associated with an atom or a group A fluonne atom in a molecule for example holds its electrons tightly and is very nonpolanzable Iodine is very polanz able... 

This result, called the Clausius-Mosotti equation, gives the relationship between the relative dielectric constant of a substance and its polarizability, and thus enables us to express the latter in terms of measurable quantities. The following additional comments will connect these ideas with the electric field associated with electromagnetic radiation ... 

Equations (10.17) and (10.18) show that both the relative dielectric constant and the refractive index of a substance are measurable properties of matter that quantify the interaction between matter and electric fields of whatever origin. The polarizability is the molecular parameter which is pertinent to this interaction. We shall see in the next section that a also plays an important role in the theory of light scattering. The following example illustrates the use of Eq. (10.17) to evaluate a and considers one aspect of the applicability of this quantity to light scattering. 

When monochromatic radiation falls on a molecular sample in the gas phase, and is not absorbed by it, the oscillating electric field E (see Equation 2.1) of the radiation induces in the molecule an electric dipole which is related to E by the polarizability... 

In the context of discussion of the Raman effect, Equation (5.43) relates the oscillating electric field E of the incident radiation, the induced electric dipole fi and the polarizability a by... 

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