Thinking outside the box: fluctuations and finite size effects

The isothermal compressibility of an interacting or non-interacting system may be extracted from the fluctuations of the number of particles in a well-chosen control volume. Finite size effects are prevalent and should be accounted for to obtain a meaningful, thermodynamic compressibility. In the traditional computational setup, where a given simulation box is replicated with periodic boundary conditions, we study particle number fluctuations outside the box (i.e. when the control volume exceeds the box itself), which bear relevant thermodynamic information. We also investigate the related problem of extracting the compressibility from the structure factor in the small wave-vector limit (k → 0). The calculation should be restricted to the discrete set of wave-vectors k that are compatible with the periodicity of the system, and we assess the consequences of considering other k values, a widespread error among beginners. (paper)