TAMie Force Field for Alkanethiols: Multifidelity Gaussian Processes for Dealing with Scarce Experimental Data

Abstract

This study extends the transferable anisotropic Mie potential (TAMie) to alkanethiols. The force field parameters are optimized by using an analytic equation of state as a surrogate model. Given the lack of experimental density data at elevated temperatures where Monte Carlo simulations have high statistical precision, the equation of state is supplemented by a linear multifidelity Gaussian process approach to bridge the temperature gap. Force field parameters are adjusted by minimizing squared deviations of calculated vapor pressures and liquid densities from experimental data of 1-propanethiol, 1-butanethiol and 1-pentanethiol leading to small mean absolute relative deviations in liquid densities and vapor pressures. The force field is transferable to higher 1-thiols, as shown for 1hexanethiol and 1-octanethiol. Individual parameter sets are provided for methanethiol and ethanethiol. The shear viscosity of pure substances is predicted in fair agreement with experimental data, considering that it is not included in the parametrization. Further, the phase behavior of binary mixtures of alkanethiols with alkanes is studied, and predictions of the TAMie model are found in excellent agreement with experimental data.