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The bond stretching, bending, stretch-bend, out of plane, and torsion interactions are called bonded interactions (intramolecular) because the atoms involved must be directly bonded or bonded to a common atom. The van der Waals and electrostatic (qq) interactions are between non-bonded atoms. In addition, Waals and electrostatic (qq) interactions exist between atoms of different molecules. The energy, coming from atoms between different molecules, is called intermolecular energy. It is important to realize that the force field is not absolute, in that not all the interactions listed in Equation (3.2) may be necessary to predict accurately the energy of a system, every time we are considering the most important forces. The total energy of a molecular system is given by the sum of the intermolecular and intramolecular interactions. Etotal =Eintramolecular + Eintermolecular (3.3) 3.2 STATISTICAL MECHANICS 3.2.1 Introduction The central question in Statistical Mechanics can be phrased as follows: if particles (atoms, molecules, electrons...) obey certain microscopic laws with specified interparticle interactions, what are the observable properties of a macroscopic system containing a large number of such particles? According to thermodynamics, a system containing a single pure substance at equilibrium can be completely characterized by three independent variables, say E, V, and N, where E is energy of the system, V the Volume and N represents the number of molecules, generally of the order of 1024. According to classical mechanics, the dynamics of each particle is defined by its three coordinates (e.g. x, y, z) and three momenta (e.g. px, py, pz) (Figure 3-1), so the previous system would require immensely greater detail: all the generalized coordinates q1 (t),q2(t)...qn (t) and 30PDF Image | MOLECULAR SIMULATION STUDIES IN THE SUPERCRITICAL REGION
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