An extended liouville equation for variable particle number systems

Abstract

It is well-known that the Liouville equation of statistical mechanics is restricted to systems where the total number of particles (N) is fixed. In this paper, we show how the Liouville equation can be extended to systems where the number of particles can vary, such as in open systems or in systems where particles can be annihilated or created. A general conservation equation for an arbitrary dynamical variable is derived from the extended Liouville equation following Irving and Kirkwood's2 technique. From the general conservation equation, the particle number conservation equation is obtained that includes general terms for the annihilation or creation of particles. It is also shown that the grand canonical ensemble distribution function is a particular stationary solution of the extended Liouville equation, as required. In general, the extended Liouville equation can be used to study nonequilibrium systems where the total number of particles can vary.