Charge distribution, from method

The third and most accurate method is that of the self-consistent field, due to Hartree(36). Here the interaction of the electrons is replaced by a central field, superposed upon the Coulomb field of the nucleus. The central field is chosen in such a way that the electrons, moving in the modified field of the nucleus according to wave mechanics, will just give rise to a charge distribution from which this central field would result on the basis of electrostatics. In contrast to the Thomas-Fermi distribution the last two methods have to be applied to every atom individually and are hence far more troublesome to handle. 

In either case, the structure of the solvation shell has to be calculated by otiier methods supplied or introduced ad hoc by some fiirther model assumptions, while charge distributions of the solute and within solvent molecules are obtained from quantum chemistry. 

The underlying principle of the PEOE method is that the electronic polarization within the tr-bond skeleton as measured by the inductive effect is attenuated with each intervening o -bond. The electronic polarization within /r-bond systems as measured by the resonance or mesomeric effect, on the other hand, extends across an entire nr-system without any attenuation. The simple model of an electron in a box expresses this fact. Thus, in calculating the charge distribution in conjugated i -systems an approach different from the PEOE method has to be taken. 

In the present work, we shall investigate the problem of the amount of correlation accounted for in the DF formalism by comparing the molecular electrostatic potentials (MEPs) and dipole moments of CO and N2O calculated by DF and ab initio methods. It is indeed well known that the calculated dipole moment rf these compounds is critically dependent on the level of theory implemented and, in particular, that introduction of correlation is essential for an accurate prediction [13,14]. As the MEP property reflects reliably the partial charges distribution on the atoms of the molecule, it is expected that the MEP will exhibit a similar dependence and that its gross features correlate with the changes in the value of dipole moment when switching from one level of theory to the other. Such a behavior has indeed been reported recently by Luque et al. [15], but their study is limited to the ab initio method and we found it worthwhile to extend it to the DF formalism. Finally, the proton affinity and the site of protonation of N2O, as calculated by both DF and ab initio methods, will be reported. 

The determination of the number of the SHG active complex cations from the corresponding SHG intensity and thus the surface charge density, a°, is not possible because the values of the molecular second-order nonlinear electrical polarizability, a , and molecular orientation, T), of the SHG active complex cation and its distribution at the membrane surface are not known [see Eq. (3)]. Although the formation of an SHG active monolayer seems not to be the only possible explanation, we used the following method to estimate the surface charge density from the SHG results since the square root of the SHG intensity, is proportional to the number of SHG active cation com-... 

This method has been used for the reconstruction of charge densities from X-ray data [1-3], for maps of nuclear densities from unpolarized neutron data [4-6] as well as for distributions of spin (magnetization) density [7-9].The density... 

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