Polarizability correction term

XYZ = XYZo + s tz + d(5) + aa where S is a polarizability correction term equal to 0.0 for non-chlorinated aliphatic solvents, 0.5 for polychlorinated aliphatics, and 1.0 for aromatic solvents. 

HB interactions, is claimed to lie in different responses to solvent polarizability effects. Likewise, in the relationship between the Ji scale and the reaction field functions of the refractive index (whose square is called the optical dielectric constant e ) and the dielectric constant, the aromatic and the halogenated solvents were found to constitute special cases." This feature is also reflected by die polarizability correction term in eq. [13.1.2] below. For the select solvents, the various polarity scales are more or less equivalent. A recent account of the various scales has been given by Marcus, and in particular of by Laurence et al., and of Ey by Reichardt. ... 

Piris and Otto (PO) achieved a reconstruction functional D[ D] satisfying the most general properties of the 2-RDM [58]. They kept the spin structure from Refs. [52, 53], but introduced a new spatial dependence in the correction term of the 2-RDM. Calculated values for polarizabilities [59], ionization energies, equilibrium geometries, and vibrational frequencies [60] in molecules were... 

Earlier literature has used the term hydrophobic bond, but it is clear from the above discussion that no special hydrophobic force exists. Nonpolar groups self-associate in water because their dispersal throughout the solvent would be entropically unfavorable. Once they come together and water is largely excluded, enthalpically favorable interactions are possible, but these are just (for nonaromatic hydrocarbons) the normal weak London forces between any polarizable groups. There is no bonding that is specifically hydrophobic. The correct term is hydrophobic effect. 

MR still is the chameleon [91] amongst the physicochemical parameters, despite its broad application in QSAR studies. It has been correlated with lipophilicity, molar volume, and steric bulk. Of course, due to its MW/q component it is indeed related to volume and size of a substituent. But two recent statements that MR is only based on these properties [91, 291] cannot be accepted. The refractive index-related correction term in MR accounts for the polarizability and thus for the size and the polarity of a certain group [158, 173, 286]. The larger the polar part of a molecule is, the larger its MR value will be. Even hydrophobic substituents have a weak enthalpic interaction due to dispersion forces, in addition to their entropic... 

These expansions serve mainly as definitions of the polarizabilities and hyperpolarizabilities as proportionality constants in the correction terms to the permanent moments. The dipole polarizability a is a second-rank tensor with nine cartesian components the dipole-quadrupole polarizability and first dipole... 

A number of static perturbations arise from internal interactions or fields, which are neglected in the nonrelativistic Born-Oppenheimer electronic Hamiltonian. The relativistic correction terms of the Breit-Pauli Hamiltonian are considered as perturbations in nonrelativistic quantum chemistry, including Darwin corrections, the mass-velocity correction, and spin-orbit and spin-spin interactions. Some properties, such as nuclear magnetic resonance shielding tensors and shielding polarizabilities, are computed from perturbation operators that involve both internal and external fields. 

These quantities are given in Table 3.2 as well. The same procedure can be followed in the case of odier X2CY molecules with X = D, F, Cl, Br and Y = O, S. The rotation-free isotope is created by setting the X-masses equal to zero. Application of the zero-mass approach in evaluating rotational correction terms to polarizability derivatives will be illustrated with an example in die second part of the book. 

Rotational correction terms to polarizability derivatives for the three molecules obtained by following the procedure described above are given in Tables 9.2, 9.3 and 9.4, respectively. 

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