Total correlation function integrals and isothermal compressibilities from molecular simulations

Abstract: Generation of thermodynamic data, here compressed liquid density and isothermal compressibility data, using molecular dynamics simulations is investigated. Five normal alkane systems are simulated at three different state points. We compare two main approaches to isothermal compressibilities: (1) fluctuation solution theory analysis of trajectories obtained from simulations to yield total correlation function integrals; and (2) the more commonly used fluctuation formula. The results show that the two approaches yield consistent values and consistent uncertainties. Also, the computations converge in approximately the same amount of time. This suggests that computation of total correlation function integrals is a route to isothermal compressibility, as accurate and fast as well-established benchmark techniques. A crucial step is the integration of the radial distribution function. To obtain sensible results, this integral must be evaluated quite accurately. A previously employed integration method fits a radial distribution function expression to data. A modification is suggested for improving the accuracy, so that more accurate (individual) total correlation function integrals are obtained. [Copyright &y& Elsevier]