Molecular polarizabilities

Since the Vuks equation correlates the macroscopic refractive index to the microscopic molecular polarizabUity, if we know refractive index, then we can calculate the molecular polarizability, or vice versa. For instance, if we know the n and data of an LC, then we can calculate its and values at different temperatures and wavelengths. 

In Equation (6.4), there is stUl an unknown parameter N the number of molecules per unit volume. However, N is equal to pNJM, where p is the LC density, M is the molecular weight, and Na is the Avogadro s number. Rearranging Equation (6.4), we find 

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The next step towards increasing the accuracy in estimating molecular properties is to use different contributions for atoms in different hybridi2ation states. This simple extension is sufficient to reproduce mean molecular polarizabilities to within 1-3 % of the experimental value. The estimation of mean molecular polarizabilities from atomic refractions has a long history, dating back to around 1911 [7], Miller and Sav-chik were the first to propose a method that considered atom hybridization in which each atom is characterized by its state of atomic hybridization [8]. They derived a formula for calculating these contributions on the basis of a theoretical interpretation of variational perturbation results and on the basis of molecular orbital theory. 

Table 7-1 lists some comparisons between experimental mean molecular polarizabilities and those estimated by Eq. (6). In this scheme, the estimation of mean molecular polarizability for acetic add needs five values, values for sp -C, for sp -C, for sp -O, for sp -O, and for a hydrogen atom. 

Table 7,1. Experimental mean molecular polarizabilities and values calculated by Eq. (6).

Until now, we have discussed the use of additivity schemes to estimate global properties of a molecule such as its mean molecular polarizability, its heat of formation, or its average binding energy to a protein receptor. 

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))... 

In many chemical applications, however, it would be more interesting to know how polarizability can stabilize a charge introduced into a molecule. Thus, rather than the global molecular property, mean molecular polarizability, a local, site-specific value for polarizability is needed. 

The molecular electronic polarizability is one of the most important descriptors used in QSPR models. Paradoxically, although it is an electronic property, it is often easier to calculate the polarizability by an additive method (see Section 7.1) than quantum mechanically. Ah-initio and DFT methods need very large basis sets before they give accurate polarizabilities. Accurate molecular polarizabilities are available from semi-empirical MO calculations very easily using a modified version of a simple variational technique proposed by Rivail and co-workers [41]. The molecular electronic polarizability correlates quite strongly with the molecular volume, although there are many cases where both descriptors are useful in QSPR models. 

Quantum chemical descriptors such as atomic charges, HOMO and LUMO energies, HOMO and LUMO orbital energy differences, atom-atom polarizabilities, super-delocalizabilities, molecular polarizabilities, dipole moments, and energies sucb as the beat of formation, ionization potential, electron affinity, and energy of protonation are applicable in QSAR/QSPR studies. A review is given by Karelson et al. [45]. 

This is not an SCRF model, as the dipole moment and stabilization are not calculated in a self-consistent way. When the back-polarization of the medium is taken into account, the dipole moment changes, depending on how polarizable the molecule is. Taking only the first-order effect into account, the stabilization becomes (a is the molecular polarizability, the first-order change in the dipole moment with respect to an electric field, Section 10.1.1). 

This induced dipole moment is independent of any dipole moment the molecule may possess in its equilibrium configuration. The molecular polarizability, a, has the properties of a tensor because both M and E are vectors. 

For a vibration to be observable in the Raman spectrum there must be a change in molecular polarizability during the vibration. 

The molecular polarizability can be considered to be the cumulation of individual bond polarizabilities. The bond polarizability is known (in simple cases) to be an approximately linear function of bond length for small amplitudes of vibration. That is, polarizability is essentially a bond property and consequently is independent of direction along any axis (or independent of sense ). 

The polarizability tensor may therefore be defined by a set of nine components which reduce in number to six because the tensor is symmetric. The physical significance of molecular polarizability is often explained in terms of the polarizability ellipsoid which is defined by the equation ... 

The antisymmetric stretching vibration. The molecule loses its original symmetry during the vibration. At the two extrema of the vibration the shapes of the molecule will be identical. Because the molecular polarizability is essentially the summation of all bond polarizabilities and is independent of direction along the internuclear axis, it will have identical values at the extrema. Consequently, the vibration is Raman inactive. 

In Appendix A, we follow the derivation of Shi and Rabitz and carry out the functional variation of the objective functional [Eq. (1)] so as to obtain the equations that must be obeyed by the wave function (vl/(t)), the undetermined Lagrange multiplier (x(0)> the electric field (e(t)). Since the results discussed in Section IV.B focus on controlled excitation of H2, where molecular polarizability must be considered, the penalty term given by Eq. (3) is used and the equations that must be obeyed by these functions are (see Appendix A for a detailed derivation) ... 

Similarly, Wei et al. [18] made analogous predictions of C < 0 using hypernetted-chain theory and incorporating molecular polarizability. However, the discussion was again restricted to the plausibility of negative C under -control. 

Guan, J., Duffy, P., Carter, J. T., Chong, D. P., Casida, K., Casida, M. E., Wrinn, M., 1993, Comparison of Local-Density and Hartree-Fock Calculations of Molecular Polarizabilities and Hyperpolarizabilities , J. Chem. Phys., 98, 4753. 

The development of the methods described in Section 9.2 was an important step in modeling polarization because it led to accurate calculations of molecular polarizability tensors. The most serious issue with those methods is known as the polarization catastrophe since they are unable to reproduce the substantial decrease of the total dipole moment at distances close to contact as obtained from ab initio calculations. As noted by Applequist et al. [49], and Thole [50], a property of the unmodified point dipole is that it may originate infinite polarization by the cooperative interaction of the two induced dipoles in the direction of the line connecting the two. The mathematical origins of such singularities are made more evident by considering a simple system consisting of two atoms (A and B) with isotropic polarizabilities, aA and c b. The molecular polarizability, has two components, one parallel and one perpendicular to the bond axis between A and B,... 

While nonbonded atom pairs will typically not come within 1A of each other, it is possible for covalently bound pairs, either directly bounds, as in 1-2 pairs, or at the vertices of an angle, as in 1-3 pairs. Accordingly it may be considered desirable to omit the 1-2 and 1-3 dipole-dipole interactions as is commonly performed on additive force fields for the Coulombic and van der Waals terms. However, it has been shown that inclusion of the 1-2 and 1-3 dipole-dipole interactions is required to achieve anistropic molecular polarizabilites when using isotropic atomic polariz-abilites [50], For example, in a Drude model of benzene in which isotropic polarization was included on the carbons only inclusion of the 1-2 and 1-3 dipole-dipole interactions along with the appropriate damping of those interactions allowed for reproduction of the anisotropic molecular polarizability of the molecule [64], Thus, it may be considered desirable to include these short range interactions in a polarizable force field. 

Thole s polarizability parameters were selected to optimize the molecular polarizabilities for a set of 16 molecules. The method was later expanded to fit 52 molecules [146], It must be emphasized that this electric-field damping method is totally independent of the polarization scheme used. For the Drude and fluctuating charge methods only /i(r) is required, whereas for methods based on induced dipoles both /i(r) and /2(r) are necessary. In the context of the induced dipole model other models were proposed since the formula of Thole does not provide enough attenuation. For example, in Ref. [152] the field is evaluated using... 

Ma BY, Lii JH, Allinger NL (2000) Molecular polarizabilities and induced dipole moments in molecular mechanics. J Comput Chem 21(10) 813—825... 

Applequist J, Carl JR, Fung K-K (1972) Atom dipole interaction model for molecular polarizability. Application to polyatomic molecules and determination of atom polarizabilities. J Am Chem Soc... 

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