Initial geometries for simulations were prepared by optimising the all-trans conformers of 8OCB and 9 at the B3LYP/6-31++G(d,p) level 9, 10 using Gaussian 16 Rev A.03. Electrostatic potentials were then calculated at the HF/6-31++G(d,p) level using Gaussian 16, before using AmberTools 19 to generate a set of RESP atomic charges and a set of GAFF version 1.81 forcefield parameters. The forcefield parameters were then converted using ACPYPE and some forcefield parameters, namely the C-C-C-C torsional parameters and the non-bonded parameters for aromatic carbon atoms, were modified to those reported to give improved results for liquid crystal molecules. Fully atomistic molecular dynamics (MD) simulations were then performed with GROMACS 2019.3. All MD simulations were run with periodic boundary conditions using 2-fs steps, and all bonds were constrained at their equilibrium lengths using the LINCS algorithm. A van der Waals cutoff of 1.2 nm was used, and the Particle Mesh Ewald method was used for longrange electrostatic interactions with a cutoff of 1.2 nm. Coordinates were written to trajectory files every 50 ps for the main simulations. For the system preparation and equilibration steps, a velocity rescaling thermostat and Berendsen barostat were used, as appropriate; for the full simulations, a Nose-Hoover thermostat 28, 29 with a 1-ps time constant and a Parrinello-Rahman barostat with a 4-ps time constant were used. Dispersion correction was used for energy and pressure, and simulation trajectories were visualised in VMD 1.9.4. Initial simulation boxes were prepared by arranging molecules onto a regular 3D grid at a spacing corresponding to a gas-phase density (<20 kg m -3 ), and doing a simulation run to allow the system to randomise, before it was compressed to a liquid-phase density (ca. 1,000 kg m -3 ).