Terahertz spectroscopy of 2,4,6-trinitrotoluene molecular solids from first principles

in Beilstein Journal of Organic Chemistry (2018), 14

We present a computational analysis of the terahertz spectra of the monoclinic and the orthorhombic polymorphs of 2,4,6-trinitrotoluene. Very good agreement with experimental data is found when using ... [more ▼]

We present a computational analysis of the terahertz spectra of the monoclinic and the orthorhombic polymorphs of 2,4,6-trinitrotoluene. Very good agreement with experimental data is found when using density functional theory that includes Tkatchenko–Scheffler pair-wise dispersion interactions. Furthermore, we show that for these polymorphs the theoretical results are only weakly affected by many-body dispersion contributions. The absence of dispersion interactions, however, causes sizable shifts in vibrational frequencies and directly affects the spatial character of the vibrational modes. Mode assignment allows for a distinction between the contributions of the monoclinic and orthorhombic polymorphs and shows that modes in the range from 0 to ca. 3.3 THz comprise both inter- and intramolecular vibrations, with the former dominating below ca. 1.5 THz. We also find that intramolecular contributions primarily involve the nitro and methyl groups. Finally, we present a prediction for the terahertz spectrum of 1,3,5-trinitrobenzene, showing that a modest chemical change leads to a markedly different terahertz spectrum. [less ▲]

Coaxial Electrospinning of Liquid Crystal-containing Poly(vinyl Pyrrolidone) Microfibers

in Beilstein Journal of Organic Chemistry (2009), 5(58), 103762558

With the relatively new technique of coaxial electrospinning, composite fibres of poly(vinylpyrrolidone) with the liquid crystal 4-cyano-4′-octylbiphenyl in its smectic phase as core material could be ... [more ▼]

With the relatively new technique of coaxial electrospinning, composite fibres of poly(vinylpyrrolidone) with the liquid crystal 4-cyano-4′-octylbiphenyl in its smectic phase as core material could be produced. The encapsulation leads to remarkable confine- ment effects on the liquid crystal, inducing changes in its phase sequence. We conducted a series of experiments to determine the effect of varying the relative flow rates of inner and outer fluid as well as of the applied voltage during electrospinning on these composite fibres. From X-ray diffraction patterns of oriented fibres we could also establish the orientation of the liquid crystal molecules to be parallel to the fibre axis, a result unexpected when considering the viscosity anisotropy of the liquid crystal kept in its smectic phase during electrospinning. [less ▲]