Roles of Repulsive and Attractive Forces in Liquids: The Optimized Random Phase Approximation
CALIFORNIA UNIV SAN DIEGO LA JOLLA DEPT OF CHEMISTRY
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The optimized random phase approximation ORPA is applied to the calculation of the thermodynamic properties and pair correlation function of simple liquids. General formulas are presented, together with results for the Lennard-Jones fluid, which are compared with Monte Carlo and molecular dynamic results. Excellent agreement is obtained for the entire single phase fluid region of the phase diagram, except for the critical region and the very low temperature vapor. The importance of separating the intermolecular potential in the proper way to obtain most rapid convergence of perturbation theories is discussed. It is concluded that the structure of simple liquids is determined mostly by the rapidly varying parts of the potential. Further, the ORPA provides an accurate theory for calculating the contributions from different forces to the structure and thermodynamics of liquids.
- Atomic and Molecular Physics and Spectroscopy