This chapter contains the essential statistical mechanics required to understand the inner workings of, and interpretation of results from, computer simulations. The microcanonical, canonical, isothermal–isobaric, semigrand and grand canonical ensembles are defined. Thermodynamic, structural, and dynamical properties of simple and complex liquids are related to appropriate functions of molecular positions and velocities. A number of important thermodynamic properties are defined in terms of fluctuations in these ensembles. The effect of the inclusion of hard constraints in the underlying potential model on the calculated properties is considered, and the addition of long-range and quantum corrections to classical simulations is presented. The extension of statistical mechanics to describe inhomogeneous systems such as the planar gas–liquid interface, fluid membranes, and liquid crystals, and its application in the simulation of these systems, are discussed.
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