Ehrenfest urn revisited: Playing the game on a realistic fluid model

The Ehrenfest urn process, also known as the dogs and fleas model, is realistically simulated by molecular dynamics of the Lennard-Jones fluid. The key variable is Δz—i.e., the absolute value of the difference between the number of particles in one half of the simulation box and in the other half. This is a pure-jump stochastic process induced, under coarse graining, by the deterministic time evolution of the atomic coordinates. We discuss the Markov hypothesis by analyzing the statistical properties of the jumps and the waiting times between the jumps. In the limit of a vanishing integration time step, the distribution of waiting times becomes closer to an exponential and, therefore, the continuous-time jump stochastic process is Markovian. The random variable Δz behaves as a Markov chain and, in the gas phase, the observed transition probabilities follow the predictions of the Ehrenfest theory.