Molecule independent particle behavior

In this chapter we review the recent history of and evidence for collective, moleculelike behavior of valence electrons in atoms and indicate some of the questions that will have to be explored in order to resolve the question of how well the electrons in atoms are described by independent-particle or collective models. We then turn the question around and ask whether atoms in a molecule could, under suitable circumstances, display independent-particle behavior, with their own one-particle angular momenta behaving like nearconstants of the motion. The larger question that emerges is then one of whether few-body systems—the valence electrons of an atom, the atoms that constitute a small polyatomic molecule, and perhaps others such as the nucleons in a nucleus, all of which have heretofore seemed nearly unrelated— share characteristics to the extent that we can devise a unifying picture of the dynamics of few-body systems that will expose their commonalities as well as their obvious differences. 

The condition for SI behavior is that the coupling work of each molecule is independent of the composition (in the P, T, N system). In the one-dimensional system, each particle sees only two hard points (the surfaces) in its neighborhood, one in front and one in its back. Hence, the average interaction free energy is independent of the sizes of its neighbors. This property is particular to the one-dimensional system. 

There are essentially three significant quantities that can be derived from the inversion of the KB theory. The first is a measure of the extent of deviation from symmetrical ideal (SI) solution behavior, A b. defined below in the next section. It also provides a necessary and sufficient condition for SI solution. The second is a measure of the extent of preferential solvation (PS) around each molecule. In a binary system of A and B, there are only two independent PS quantities these measure the preference of, say, molecule A to be solvated by either A or B molecules. Deviations from SI solution behavior can be expressed in terms of either the sum or difference of these PS quantities. Finally, the Kirkwood-Buff integrals (KBIs) may be obtained from the inversion of the KB theory. These provide information on the affinities between any two species for instance, PaGaa measures the excess of the average number of A particles around A relative to the average number of A particles in the same region chosen at a random location in the mixture. All these quantities can be obtained from the KB integrals. 

---