Overlap volumes

For hard spheres, the coefficients are independent of temperature because the Mayer/-fiinctions, in tenns of which they can be expressed, are temperature independent. The calculation of the leading temiy fy) is simple, but the detennination of the remaining tenns increases in complexify for larger n. Recalling that the Mayer /-fiinction for hard spheres of diameter a is -1 when r < a, and zero otherwise, it follows thaty/r, 7) is zero for r > 2a. For r < 2a, it is just the overlap volume of two spheres of radii 2a and a sunple calculation shows tliat... 

Molecular Shape Analysis. Once a set of shapes or conformations are generated for a chemical or series of analogs, the usual question is which are similar. Similarity in three dimensions of collections of atoms is very difficult and often subjective. Molecular shape analysis is an attempt to provide a similarity index for molecular structures. The basic approach is to compute the maximum overlap volume of the two molecules by superimposing one onto the other. This is done for all pairs of molecules being considered and this measure, in cubic angstroms, can be used as a parameter for mathematical procedures such as correlation analysis. 

As stated above, Afd is related to the contact pair potential Afg(0). In a floe, each particle is in close contact with z other particles. If A/a is small, the z lens-shaped overlap volumes (see Figure A) surrounding each particle do not overlap with each other, and Afd equals zAf (0)/2 where Afg(0) is given by Equation 8. For higher values of A/a, the lenses overlap partly, and Afd < zAfs(0)/2. Above a certain value of A/a (which depends on the packing of the particles in the floe), there is no polymer left within the interstices of the floe and all the solvent in the floe is within a distance A from the surface of at least one particle. Then the volume of solvent which is transferred towards the solution when a particle is added to the floe is readily calculated. 

For small chains in solution the translational diffusion significantly contributes to the overall decay of Schain(Q>0- Therefore precise knowledge of the centre of mass diffusion is essential. Combing dynamic light scattering (DLS) and NSE revealed effective collective diffusion coefficients. Measurements at different concentrations showed that up to a polymer volume fraction of 10% no concentration dependence could be detected. All data are well below the overlap volume fraction of (p =0.23. Since no -dependence was seen, the data may be directly compared with the Zimm prediction [6] for dilute solutions ... 

There is another type of free energy change that can be considered within the overlap volume in addition to the concentration effect considered by the Flory-Krigbaum theory. This additional contribution to AGlens is likely to be more important for d < 5RS and should be considered when the outcome of the encounter is not determined by the initial approach of the colliding particles. This contribution arises from an elastic response by the adsorbed polymer, effectively pushing the approaching particles apart. 

For non-overlapping volumes, r > Ao, the fluctuations in particle numbers are statistically independent and thus... 

What is the size of the overlapping volume The complete independence of the constant in Equation 1 from the degree of polymerization shows that the overlapping volume always consists of the same portion of the volume of the polymer coil (12). This can be easily understood by assuming that two polymer coils are able to migrate nearly unhindered through each other. Then the mean depth of permeation and, therefore, the time of overlapping is determined only by the statistics of the free Brownian motion. Equation 1 is based on this assumption. 

Figure 3. Overlapping volume of two radical polymer chains represented by equivalent spheres...

The overlapping occurs within a distance defined by 2 (depending on the angle y). Taking the mean of over all angles y gives a mean overlapping volume. 

Figure 2. (a) Interaction of small spherical molecules. The molecule at 2, on the inner edge of a square potential well of width x, is in contact with the central molecule 1. At 2 it is on the outer edge of the well. The radius 2r defines the exclusion volume around the central molecule the shell between radius 2r and (2r+x) defines its interaction volume. (6) Interaction of spherical shell-molecules. Atoms 1 and 2 on their respective shells are in contact on the inner edge of a square well of width x. Atoms 1 and 2 are beyond the outer edge of the well. If the shell-atoms are taken as uniformly smeared around the shells, the energy of interaction between the molecules should be approximately proportional to the overlap volume Va, the region in which the shells are closer than x. 

The formation of mixed crystals by means of a solid-state reaction occurs under kinetic control and may be subject to different constraints than the formation of mixed crystals grown closer to equilibrium conditions from the melt or from solvents. However, whether or not mixed crystallization is possible, and to what extent, is still determined by the structural similarity of the reactant and the product. Kitaigorodskii suggested guidelines based on a volume analysis which indicate that chemically compatible compounds which have optimized overlapping volumes larger than ca. 75% are likely to form solid solutions [66],... 

In one of the limiting cases, the free polymer is allowed to penetrate the adsorbed layer around the particles. One may note that when the free polymer and the adsorbed polymer are both present in the steric layer around the particle, the interactions between the two must be taken into account while evaluating the in-terparticle forces. However, in the absence of a detailed knowledge of the structure of the adsorbed layer, it is difficult to evaluate this contribution to the interaction potential. Then, the situation is similar to the one considered by Asakura and Oosawa (16), and the force of attraction between two bare particles of radius a in the presence of free polymer molecules of radius / can be expressed as the product of the osmotic pressure Pmm and the area of the intersection of the two overlapping volumes ... 

Eor the case of a hard-core solute the condition / 7 0 sharply defines the overlap volume. Generalize the combinatorial results above by considering the quantity... 

---