| 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  [University of Luxembourg > Faculty of Science, Technology and Communication (FSTC) > Physics and Materials Science Research Unit >] | |
| 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 |
| File(s) associated to this reference | ||||||||||||||
|
Fulltext file(s):
| ||||||||||||||
All documents in ORBilu are protected by a user license.
