Article (Scientific journals)
Terahertz spectroscopy of 2,4,6-trinitrotoluene molecular solids from first principles
Azuri, Ido; Hirsch, Anna; Reilly, Anthony et al.
2018In Beilstein Journal of Organic Chemistry, 14, p. 8
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Keywords :
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
Abstract :
[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.
Disciplines :
Physics
Author, co-author :
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
External co-authors :
yes
Language :
English
Title :
Terahertz spectroscopy of 2,4,6-trinitrotoluene molecular solids from first principles
Publication date :
09 February 2018
Journal title :
Beilstein Journal of Organic Chemistry
ISSN :
1860-5397
Publisher :
Beilstein-Institut, Germany
Volume :
14
Pages :
8
Peer reviewed :
Peer Reviewed verified by ORBi
Focus Area :
Physics and Materials Science
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