Atomic charges from different models

Another recent semiempirical charge model [166] is based on a different concept Here the usual atomic charges from an established semiempirical method (e.g., AMI or PM3) are taken as the starting point for a subsequent semiempirical mapping which further refines these charges such that physical observables calculated from these modified... 

It is also possible to explain, from hydration models, the differences between equally-charged cations, such as the alkali metals = 73,5, = 50,1 land 38.68, all in units of mor cm ). From atomic... 

In contrast to the point charge model, which needs atom-centered charges from an external source (because of the geometry dependence of the charge distribution they cannot be parameterized and are often pre-calculated by quantum mechanics), the relatively few different bond dipoles are parameterized. An elegant way to calculate charges is by the use of so-called bond increments (Eq. (26)), which are defined as the charge contribution of each atom j bound to atom i. 

Exact solutions to the electronic Schrodinger equation are not possible for many-electron atoms, but atomic HF calculations have been done both numerically and within the LCAO model. In approximate work, and for molecular applications, it is desirable to use basis functions that are simple in form. A polyelectron atom is quite different from a one-electron atom because of the phenomenon of shielding", for a particular electron, the other electrons partially screen the effect of the positively charged nucleus. Both Zener (1930) and Slater (1930) used very simple hydrogen-like orbitals of the form... 

Given the diversity of different SCRF models, and the fact that solvation energies in water may range from a few kcal/mol for say ethane to perhaps 100 kcal/mol for an ion, it is difficult to evaluate just how accurately continuum methods may in principle be able to represent solvation. It seems clear, however, that molecular shaped cavities must be employed, the electiostatic polarization needs a description either in terms of atomic charges or quite high-order multipoles, and cavity and dispersion terms must be included. Properly parameterized, such models appear to be able to give absolute values with an accuracy of a few kcal/mol." Molecular properties are in many cases also sensitive to the environment, but a detailed discussion of this is outside the scope of this book. ... 

Examination of the multipole populations gives no indication of the discrepancy observed in the model maps, all populations from parallel refinements agreeing to within two esd s (Table 5). The one striking exception is the monopole population (P,) for carbon. This must be a simple difference in the partitioning of the charge density between atom centers in the model as there is no discernible difference in the model maps around the carbon position. 

Indeed, both expressions predict quadratic dependence of AA on the dipole moment of the solute. As in the previous example, it is of interest to test whether this prediction is correct. Such a test was carried out by calculating AA for a series of model solutes immersed in water at different distances from the water-hexane interface [11]. The solutes were constructed by scaling the atomic charges and, consequently, the dipole moment of a nearly spherical molecule, CH3F, by a parameter A, which varied between 0 and 1.2. The results at two positions - deep in the water phase and at the interface - are shown in Fig. 2.3. As can be seen from the linear dependence of A A on p2, the accuracy of the second-order perturbation theory... 

It is not possible to say which method provides the better atomic charges. Each offers distinct advantages and each suffers from disadvantages. The choice ultimately rests with the application and the level of comfort . Having selected a method, stick with it. As shown from the data in Table 16-1, atomic charges calculated from the two different schemes and from different quantum chemical models, may be significantly different. 

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