Simulation of the density of states in isothermal and adiabatic ensembles

This paper provides a unified treatment of the fundamental methods used to obtain the density of states via molecular simulations with isothermal ensembles (IEs) and adiabatic ensembles (AEs). Our analysis and results show that provides a natural bridge to go back and forth between IE and AE simulation data. They also underline the difference between the density of states of potential energy macrostates and that of total energy macrostates Omega, even though both provide access to the thermodynamic properties of the system. Visited-states approaches and transition matrix methods are described and applied to the Lennard-Jones fluid to target omega and Omega as functions of energy and volume macrostates. It is shown that one can obtain omega via a generalized acceptance-ratio formula that is applicable regardless of the conditions at which the ensemble is simulated. In this way, one can obtain while performing conventional IE or AE simulations, and do it at no extra cost and with a higher accuracy than is achievable with histogram methods.