Atomistic simulations of liquid crystal mixtures of alkoxy substituted phenylpyrimidines 2PhP and PhP14

We study liquid crystal mixtures of alkoxy substituted phenylpyrimidines 2-4-(butyloxy)phenyl]-5-(octyloxy)pyrimidine (2PhP) and 2-4-(tetradecyloxy)phenyl]-5-(tetradecyloxy)pyrimidine (PhP14) using molecular dynamics simulations at the all atom level. The molecular length of PhP14 is 1.8 times that of 2PhP, resulting in an interesting binary mixture phase diagram. Our simulations are composed of 1000-1600 molecules for a total of 80,000-130,000 atomic sites, with total simulation times of 60-100 ns. We first show that a pure 2PhP system self-assembles into isotropic, nematic, smectic A and smectic C phases, and a pure PhP14 system self-assembles into isotropic and smectic C phases. Binary mixtures of PhP14 and 2PhP display a stabilization of the smectic A phase at the expense of the smectic C and nematic phases. We determine that the concentration-induced phase transition from the smectic C to the smectic A phase in the mixture is driven by an out-of-layer fluctuation arrangement of the molecules. We also observe that the tilt angle in the smectic C phases formed in the mixtures is concentration dependent. The results of our simulations are in good agreement with the experimental findings of Kapernaum et al. J. Org. Chem. 5, 65 (2009)], thus showing that atomistic simulations are capable of reproducing the phase behavior of liquid crystal mixtures and can also provide microscopic details regarding the mechanisms that govern phase stability.