Pulling simulation predicts mixing free energy for binary mixtures.

Abstract

Predicting the mixing free energy of mixing for binary mixtures using simulations is challenging. We present a novel molecular dynamics (MD) simulation method to extract the chemical potential <i>μ</i>(<i>X</i>) for mixtures of species A and B. Each molecule of species A and B is placed in equal and opposite harmonic potentials ±(1/2)<i>U</i>_ex(<i>x</i>) centered at the middle of the simulation box, resulting in a nonuniform mole fraction profile <i>X</i>(<i>z</i>) in which A is concentrated at the center, and B at the periphery. Combining these, we obtain <i>U</i>_ex(<i>X</i>), the exchange chemical potential required to induce a given deviation of the mole fraction from its average. Simulation results for <i>U</i>_ex(<i>X</i>) can be fitted to simple free energy models to extract the interaction parameter <i>χ</i> for binary mixtures. To illustrate our method, we investigate benzene-pyridine mixtures, which provide a good example of regular solution behavior, using both TraPPE united-atom and OPLS all-atom potentials, both of which have been validated for pure fluid properties. <i>χ</i> values obtained with the new method are consistent with values from other recent simulation methods. However, the TraPPE-UA results differ substantially from the <i>χ</i> obtained from VLE experimental data, while the OPLS-AA results are in reasonable agreement with experiment, highlighting the importance of accurate potentials in correctly representing mixture behavior.