We have applied a recently developed general purpose acetonitrile force field based on first-principles calculations to simulate acetonitrile in the gas phase at different temperatures and densities. These conditions range from nearly ideal to real gas phase behavior and condensation. The molecular dynamics simulation results agree fairly well with the experimental studies available in the literature on the gas samples. The structural analysis of aggregates and their associated interaction energies is examined and related to the early model proposed on molecular association and equilibrium determining the non-ideal behavior. The formation of dimers is mainly responsible for the non-ideal behavior of the gas at very low density, confirming suggested models based on previous experimental studies. However, when the density of the sample rises, the level of aggregation increases and the simple concept of dimerization does not hold anymore. The real behavior adopted by the gas is related to the distribution of molecular structures observed. The macroscopical view of a real gas as a generic interparticle interaction system without a defined form may then be rationalized on the basis of a defined molecular association originated by a distribution of aggregates at the low density regime. The sample with the highest density (∼1.4 × 103 mol m-3) at the lowest temperature exhibits a massive aggregation where most of the acetonitrile (ACN) molecules in the simulation box form a big cluster. Its radial distribution function is similar to that of the liquid ACN. This strongly inhomogeneous distribution in the box can be considered a condensation in the gas phase under specific density-T conditions. This formation opens the door to the potential tuning of its solvent properties as a function of its size in these nanodroplets that in turn are controlled by the density-T conditions.
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