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Statistical Thermodynamics. Lecture 6 : Imperfect Gases. Dr. Ronald M. Levy ronlevy@temple.edu. 1. 2. 3. 4. 5. Pair potential. Mayer F function. 6. Mayer F function. In terms of Mayer f function, the first 2 Virial coefficient:. 7. Cluster diagram and star diagram. 3. 3. 3. 3.
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Statistical Thermodynamics Lecture 6: Imperfect Gases Dr. Ronald M. Levy ronlevy@temple.edu
Pair potential Mayer F function 6
Mayer F function In terms of Mayer f function, the first 2 Virial coefficient: 7
Cluster diagram and star diagram 3 3 3 3 3 Numbered circles represent particles whose coordinates we integrate over the bond between pairs of circles means particles are connected by a Mayer f function. All the Virial coefficients can be expressed in terms of a special set of cluster, These are called doubly connected, or star diagram. 1 2 1 1 1 1 1 2 2 2 2 2 Cluster diagrams Not doubly connected Not star diagram Doubly connected Star diagram Note: There are 2 topologically distinct cluster diagrams for 3 particles, there us 1 star diagram and 3 which is not 8
All star diagram for j+1 particles. (The sum of all products of f functions that connect 1,2,…,j+1 molecules such that the cluster are connected so that the removal of any point, along with all lines to that point, still results in a connected graph) Star diagram for 4 particles: 1 1 1 1 2 2 4 4 3 4 2 3 3 2 4 4 9
Hard sphere potential: Very important theoretically, can get exact results! Starting point for ##### very important for liquids 𝜎/2 10
Square well potential For square well potential: 11