Concept theoretical shortcomings

This discussion could be conducted in two ways. First, we could try to deduce structural information from experimental facts through unequivocal mathematical calculations. This would be most satisfying and certainly constitutes the ultimate goal for structural studies. Unfortunately, divergencies of opinions currently observed show that we are still far from such achievement. One important reason for these difficulties may be that quantum mechanical treatment of d orbitals has not reached the precision attained for s and p orbitals. So, in many cases, it cannot be said whether discrepancies between experience and theory are due to inadequacy of theoretical concepts or to shortcomings of mathematical tools. 

The justification of jr-electron theories has been repeatedly questioned during recent years indeed, it has become almost fashionable to emphasize the shortcomings of the cr—it separation and the non-validity of the theories based upon it. These are, in fact, approximations and cannot be expected to lead to unconditionally reliable conclusions. However, the numerical results that have provoked the criticisms in question are not a necessary consequence of the a—it separation and the related approximations. Therefore, we shall begin by restating and clarifying the basic concepts on which the whole question of the a—it separation rests. We shall consider the conditions under which the electrons of a molecule can be classified into a and it electrons and indicate what should be understood be a—7i separation and what are the limitations of this approximation. We shall show that the most important part of th e a—n interaction is usually taken into accound within the a—n separation scheme and, finally, discuss whether the a—it interaction has a significant effect on the theoretical predictions made for the physical properties of unsaturated molecules (ionization potentials, electronic spectra, charge densities and dipole moments etc.). 

The shortcomings of the phantom network concepts have stimulated a number of attempts to find theoretically a more satisfactory elastic free energy function to describe the properties of elastomers at different states of deformation. The efforts to explain the real network behaviour by a special non-topological mechanism can be divided into four types. The first group considered intra- and intermolecular effects los-ni) wjtii these assumptions it is hard to explain values of the Mooney-Rivlin parameter which are of the order of the corresponding Cj parameter. 

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