Hydrogen-bond networks in linear, branched and tertiary alcohols

Molecular dynamics simulations are used to determine the hydrogen-bond networks formed by 54 linear and branched alcohols containing 5–20 carbon atoms, and the results show systematic differences in their hydrogen-bonded structures, depending both on hydroxyl group position and the alcohol's molecular weight. The hydrogen-bonded networks within these pure solvents correspond with experimentally determined water capacities for solvents in four main structural classes. These categories are: primary alcohols, secondary alcohols, tertiary alcohols, and alcohols with the branching point removed from the hydroxyl group. Each of these structural classes exhibits unique behavior in the correlation between the extended hydrogen-bond networks and observed capacities for water.