Simulation of Linear and Cyclic Alkanes with Second-Order Møller-Plesset Perturbation Theory through Adaptive Force...

Predicting ensemble properties, such as density and heat of vaporization, of small hydrocarbons is challenging due to the dispersion-dominated weak interactions between these molecules. With the adaptive force matching (AFM) method, the bonded and short-range nonbonded interactions are fitted to second-order Møller-Plesset perturbation theory (MP2) references computed with the def2-TZVP basis set. The dispersion is modeled using symmetry adapted perturbation theory (SAPT) at MP4 accuracy using the def2-TZVPD basis set. A new charge matrix decomposition technique is described to obtain partial charges in AFM. Although the models developed do not have any empirical parameters, several properties of the resulting models are compared with experiments as validations. The density, heat of vaporization, pressure dependence of density, diffusion constants, and surface tensions all show quantitative agreement with experiments. Although the density shows a very small systematic error, which could be due to missing three-body dispersion, the heat of vaporization agrees with experiments of within 0.5%. The paper shows that AFM can be used as a reliable tool to enable simulations at post-Hartree-Fock quality at the cost of molecular mechanics force fields.