Reference : Terahertz spectroscopy of 2,4,6-trinitrotoluene molecular solids from first principles |
Scientific journals : Article | |||
Physical, chemical, mathematical & earth Sciences : Physics | |||
Physics and Materials Science | |||
http://hdl.handle.net/10993/37901 | |||
Terahertz spectroscopy of 2,4,6-trinitrotoluene molecular solids from first principles | |
English | |
Azuri, Ido [Weizmann Institute of Science, Rehovoth 76100, Israel > Department of Materials and Interfaces,] | |
Hirsch, Anna [Weizmann Institute of Science, Rehovoth 76100, Israel] | |
Reilly, Anthony [School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland] | |
Tkatchenko, Alexandre ![]() | |
Kendler, Shai [] | |
Hod, Oded [] | |
Kronik, Leeor [] | |
9-Feb-2018 | |
Beilstein Journal of Organic Chemistry | |
Beilstein-Institut | |
14 | |
8 | |
Yes (verified by ORBilu) | |
International | |
1860-5397 | |
Germany | |
[en] density functional theory ; THz spectroscopyAbstract 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 | |
[en] 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. | |
Researchers ; Professionals ; Students ; General public ; Others | |
http://hdl.handle.net/10993/37901 | |
10.3762/bjoc.14.26 |
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