Determination of tilt angle and its behavior in chiral smectic phases by exploring molecular conformations using complementary methods.

Density functional theory (DFT) calculations and x-ray diffraction techniques were employed to evaluate the value of the tilt angle in ferroelectric smectic C^{} and antiferroelectric smectic C_{A}^{} phases. Five homologues from the chiral series denoted as 3FmHPhF6(m=2,4,5,6,7), based on 4-(1-methylheptyloxycarbonyl) phenyl 4'-octyloxybiphenyl-4-carboxylate (MHPOBC), were studied. Two types of conformations for the nonchiral terminal chain (fully extended and gauche) and three types of deviation from the rodlike shape of the molecules (hockey stick, zigzag, and C shape) were computationally considered. The nonlinear shape of the molecules was accounted for by introducing a shape parameter δΘ. We observe that calculations of the tilt angle which consider the C-shaped structures, in both the fully extended or gauche conformations, lead to good agreement with the values of the tilt angle obtained from electro-optical measurements below the saturation temperature. The results allow us to conclude that such structures are adopted by molecules in the examined series of smectogens. Additionally, this study proves the presence of the standard orthogonal SmA^{} phase for the homologues with m=6, 7, and the de Vries SmA^{} phase for m=5.