Association effects in pure methanol via Monte Carlo simulations. I. Structure

A methodology for the determination of the oligomers residing in a pure associated fluid was developed in the framework of the molecular simulation technique. First, the number of hydrogen bonds between each pair of molecules of the fluid is computed by using a specific criterion to define the hydrogen bonding formation. Secondly, sets of molecules linked by hydrogen bonds are identified and classified as linear chains, cyclic aggregates, branched linear chains, branched cyclic aggregates, and the rest of clustering. The procedure is applied over all the configurations produced in usual Monte Carlo simulations and allows the computation of the following properties characterizing the structure of the fluid: the fraction of molecules in the monomer or associated state, the fraction of each type of aggregate with a given size (and of molecules belonging to them), and the most probable and the average cluster size for each type. In addition, the degree of branching in branched linear chains and the type of ring in branched cyclic clusters can be obtained. In this work, all these quantities were computed for OPLS methanol using NpT Monte Carlo simulations at atmospheric pressure for 298.15 K (room conditions) and from 800 K to 350 K (gas phase), and along several supercritical isobars: 25, 50, 100, 200, and 500 MPa from 250 K to 1000 K. An analysis of the results has provided a comprehensive structural picture of methanol over the whole thermodynamic state space.