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 mailto [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

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