Experimentally obtained J tot couplings of 2-methoxy-ethanol at 25 °C and 1,2-dimethoxyethane at 40 °C were taken from Refs. and , respectively. For each compound, 255 starting structures were obtained with the KDG conformer generator and optimized for all solvent and implicit-solvent model combinations using the B3LYP functional with the TZVP basis set and a D4 correction . The minimized structures were subsequently sorted based on their ascending free energies, and the ensemble was pruned using MDTraj (version 1.9.7) based on the all-atom RMSD with a threshold of 0.05 nm. The resulting conformers in the ensemble were assigned to the gauche-conformer if the central dihedral angle (see Fig. ) was between -2.1 rad and 2.1 rad, and to the trans-conformer otherwise. The population of the trans-conformer was then calculated according to the assigned free energies.