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MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION

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MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION ( molecular-simulation-studies-insupercritical-region )

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These configurational changes take place at constant total energy so that there is an interconversion of kinetic and potential energy resulting from the changes in configuration. The calculations involved can be summarised in the form of a table such as: r1 r2 P.E ... ... The potential energy surface considered in this section are based on the Born- Oppenheimer separation of nuclear and electronic motion (Born and Oppenheimer, 1927; Hirst, 1985). For a non-linear molecule, consisting of N atoms, the potential energy surface depends on 3N-6 independent coordinates (Martin and Martin J.Field, 2000), and depicts how the potential energy changes as relative coordinates of the atomic nuclei involved in the chemical reaction are varied. An analytic function, which represents a potential energy surface, is called potential energy function. Understanding the relationship between properties of the potential energy surface and the behaviour of the chemical reaction is a central issue in chemical kinetics. Let us go back to considering the simplest possible reaction, that of an atom, A, reacting with a diatomic, BC. Then only two distances, r and r are needed to AB BC specify completely the arrangement of the atoms and so the P.E. surface is just a function of two variables, and we have a chance of being able to visualize it. In Figure 2-1, the reactants, A+BC, are found in the upper left part of the surface ( r large, r  equilibrium separation). The products, AB+C, are found in the lower AB BC right part of the diagram ( r large, r  equilibrium separation). The form of the BC AC surface is two valleys meeting at right angles, one starting at the products and one at the reactants. As we ‘walk’ up the valley away from the reactants the valley floor rises up; the same thing happens as we ‘walk’ away from the products. 17

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