To encompass the region of parameter space in Table for typical OSCs, values of κ of 0.30, 0.35, 0.40, 0.45, and 0.50, and κ of 0.15, 0.20, 0.25, and 0.30 were used. Additional κ values of 0.50 and 0.70 were examined for certain systems to access points with κ > κ, as interfacial behaviour has previously been predicted to exhibit a transition around κ/κ = 1 in some circumstances. Several systems with κ = 1.2 were also studied to examine the behaviour when side-side interactions are stronger than faceface ones. While side-side interactions that are stronger than the face-face ones are not typical of OSCs-like molecules, they can potentially be accessed through, for example, functionalisation of the aromatic core and may present an interesting means of tuning interfacial orientation. The systems with κ > 1 in this work had weaker face-face interactions than the systems with κ < 1 in order to maintain an isotropic bulk fluid as the side-side interactions were increased, meaning face-face interactions were weaker than would be the case for a typical OSC. As the alignment at both solid and vapour interfaces is expected to depend on temperature, due to competition between excluded-volume entropic effects and attractive intermolecular interactions, several temperatures between 0.56 and 0.84ε/k B were studied, corresponding to a temperature range of 507-761 K for the representative OSC systems described above, encompassing a range of temperatures where the OSCs-type molecules that are represented by these GB parameters are liquid. A full list of the specific systems studied is given in the ESI, Table .