The Structure of Liquid Methanol

A combination of density functional calculations of molecular clusters with a quantum cluster equilibrium (QCE) model provides evidence that liquid methanol is dominated by cyclic and/or lasso structures. Only cluster populations including these structures fit the measured thermodynamic and spectroscopic properties, such as heat of vaporization, heat capacity, NMR chemical shifts, and quadrupole coupling constants. On the other hand, cluster populations comprising open‐chain structures fail to reach the experimental values: the heat of vaporization is about 10 kJ mol − 1 too low, and the proton chemical shift is insufficiently downfield‐shifted by about 1 ppm.