In order to estimate a clearing point in these MD simulations of 8OCB and 9, a series of small simulations of 6 × 6 × 6 = 216 molecules were performed. Each system was allowed to randomise for 40 ps at low density at 298 K with no pressure coupling (final P2 = 0.1), and then it was compressed rapidly at a nominal pressure of 50,000 bar until a liquid-like density was reached. The condensed, randomised phase was allowed to stabilise at 1 bar, before equilibrating at 353 K (8OCB) or 358 K (9). A 500-ns simulation was then run, during which each system formed a fairly stable smectic A phase. Subsequently, 100-ns simulations were run from the final coordinates at a range of temperatures at ca. 10 K intervals both higher and lower than those at which the 500-ns run had been performed, and with isotropic pressure coupling at 1 bar. The orientational order parameters (P2) determined as a function of temperature (T) were fitted to a Haller type equation, P2 = [1 -(T/Tc)] β , where Tc gives an estimate of the clearing point of the system in the simulation and β is an empirical parameter. The data and fits from these small simulations are shown in Figure , and gave estimated Tc values of ca. 395 and 400 K for 8OCB and 9, respectively, in these simulated systems. The larger simulations presented in the main text were performed at temperatures of 369 and 374 K for 8OCB and Cyc-5OCB, respectively, both corresponding to T/Tc ≈ 0.934, which was chosen to be in the experimental smectic A range for 8OCB. Each of the larger runs was prepared as a low-density 3D grid of 12 × 12 × 10 = 1440 molecules in an approximately cubic simulation box. The initial, ordered system was simulated for 70 ps at a nominal pressure of 10 bar to allow the system to randomise (final P2 = 0.04), and it was then compressed at a nominal pressure of 50,000 bar until a liquid-like density was reached.