Thermodynamic Properties of Multicomponent Mixtures From the Solution of Groups Approach to Direct Correlation Function Solution Theory

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The important aspect of this approach is that the groups are dealt with as if they were all indepen- dent. This is not physically the situation. The dependence is caused by the intramolecular correlations, and they must be properly accounted for to yield an accurate model.
Originally it was believed that the RISM theory took account of this behavior, but as was mentioned in the preceding section, this is not true. Even the proper integral equation direct correlation functions, equation 7-3, whi
...le short ranged, still involve intramolecular correlations due to third body effects. Cummings and Sullivan (1982a) explicitly show that while the h ag (r) functions are purely intermolecu- o "*" lar quantities that the c ag (r) are not.
The exact resummation of the cluster expansion for h g (r) shown by Chandler et al. (1982) suggests a way around the aforementioned difficulties. It should be possible to define a set of direct correlation functions, labeled here as c g (r), that include only intermolecular effects.


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