Onsager-Lorentz theory

In order to formulate a theory for the evaluation of vibrational intensities within the framework of continuum solvation models, it is necessary to consider that formally the radiation electric field (static, Eloc and optical E[jc) acting on the molecule in the cavity differ from the corresponding Maxwell fields in the medium, E and Em. However, the response of the molecule to the external perturbation depends on the field locally acting on it. This problem, usually referred to as the local field effect, is normally solved by resorting to the Onsager-Lorentz theory of dielectric polarization [21,44], In such an approach the macroscopic quantities are related to the microscopic electric response of... 

From the point of view of theory, the formulae of Table 2.6 are equally applicable to both gas and condensed phase samples, as they include the local field factors, which account for local modifications to the Maxwell fields due to bulk interactions within the Onsager-Lorentz model. 

Continuum models have a long and honorable tradition in solvation modeling they ultimately have their roots in the classical formulas of Mossotti (1850), Clausius (1879), Lorentz (1880), and Lorenz (1881), based on the polarization fields in condensed media [32, 57], Chemical thermodynamics is based on free energies [58], and the modem theory of free energies in solution is traceable to Bom s derivation (1920) of the electrostatic free energy of insertion of a monatomic ion in a continuum dielectric [59], and Kirkwood and Onsager s... 

Among the few determinations of of molecular crystals, the CPHF/ INDO smdy of Yamada et al. [25] is unique because, on the one hand, it concerns an open-shell molecule, the p-nitrophenyl-nitronyl-nitroxide radical (p-NPNN) and, on the other hand, it combines in a hybrid way the oriented gas model and the supermolecule approach. Another smdy is due to Luo et al. [26], who calculated the third-order nonlinear susceptibility of amorphous thinmultilayered films of fullerenes by combining the self-consistent reaction field (SCRF) theory with cavity field factors. The amorphous namre of the system justifies the choice of the SCRF method, the removal of the sums in Eq. (3), and the use of the average second hyperpolarizability. They emphasized the differences between the Lorentz Lorenz local field factors and the more general Onsager Bbttcher ones. For Ceo the results differ by 25% but are in similar... 

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