The conformational preference of the two small molecules 2-methoxy-ethanol and 1,2-dimethoxyethane (Fig. ) does not simply follow the dielectric permittivity of the solvent but is rather governed by explicit-solvent effects such as hydrogen bonding, making them an ideal test case. For both compounds, the conformational ensemble can be described based on the rotational state of the central torsion angle (Fig. ). In Refs. and , 1 H-NMR measurements were conducted that allowed the determination of a total scalar coupling J tot of the α proton of the methoxy group, whose magnitude is directly related to the central torsions populations in different solvents. The conformers of the two compounds were evaluated using a higher level of theory as the molecular balances with the B3LYP functional and def2-TZVP basis set . Again, the three different implicit-solvent models were used in the QM calculations to optimize the two compounds in the ten solvents for which J tot value had been determined experimentally. The correlation between the predicted population of the trans-conformer and the experimentally observed J tot is shown in Fig. .