The molecular structure and orientation of antiferroelectric liquid crystal using the density-functional theory and two-dimensional correlation-polarized infrared spectroscopy.

The structure and vibrational frequencies of the chiral antiferroelectric liquid-crystal molecule, 4-(1-methyheptyloxycarbonyl) phenyl-4-(4′-octyloxy) benzoate (MHOCPOOB), have been calculated using the density-functional theory (DFT) with the Becke-3 Lee–Yang–Parr/6-31G(d,p) level. The observed vibrational spectra have been resolved and assigned in detail by comparison to the computed values. The results indicate that the computed and observed spectra are in good agreement with each other. The stable molecular structure obtained with the DFT theory shows that the two hydrocarbon chains are all-trans zigzag conformer and nearly perpendicular to each other. The orientation of the mesogen part and the hydrocarbon chains for MHOCPOOB in the Sm–CA* phase are investigated by employing the polarization-angle-dependent infrared spectra in the electric-field induced and the two-dimensional correlation spectroscopy. After combining the experimental and theoretical results, it can be concluded that the azimuth of the achiral and chiral chains is opposite to each other, the orientation of the achiral chain is almost the same direction as the mesogen core, and the orientation of the chiral chain is nearly perpendicular to the mesogen part. The achiral and chiral CH2 chains are both a probable all-trans zigzag conformer. [ABSTRACT FROM AUTHOR]