Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

Damarla Ganesh; Elaprolu Narsimha Rao; Mottamchetty Venkatesh; Kommu Nagarjuna; Ganapathy Vaitheeswaran; Akhila K Sahoo; Anil K Chaudhary

doi:10.1021/acsomega.8b03383

Time-Domain Terahertz Spectroscopy and Density Functional Theory Studies of Nitro/Nitrogen-Rich Aryl-Tetrazole Derivatives

ACS Omega. 2020 Feb 7;5(6):2541-2551. doi: 10.1021/acsomega.8b03383. eCollection 2020 Feb 18.

Authors

Damarla Ganesh¹, Elaprolu Narsimha Rao¹, Mottamchetty Venkatesh^{1

2}, Kommu Nagarjuna¹, Ganapathy Vaitheeswaran^{1

1}, Akhila K Sahoo^{1

1}, Anil K Chaudhary¹

Affiliations

¹ Advanced Center of Research in High Energy Materials (ACRHEM), School of Physics, and School of Chemistry, University of Hyderabad, Prof. C. R. Rao Road, Gachibowli, Hyderabad 500 046, Telangana, India.
² The Guo China-US Photonics Laboratory, State Key Laboratory of Applied Optics, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, Changchun 130033, China.

Abstract

The paper reports the time-domain THz spectroscopy studies of noncentrosymmetric energetic nitro/nitrogen-rich aryl-tetrazole high-energy molecules. The fingerprint spectra in the THz domain reveal the role of different functional groups attached to position "1" of the tetrazole moiety, which controls the energetic properties. These responses are deliberated through density functional theory (DFT) calculations. The synthesized aryl-tetrazoles exhibit high positive heat of formation (369-744 kJ/mol), high detonation velocities, and pressures (D _v: 7734-8298 m·s^-1; D _p: 24-28 GPa) in comparison to the noncentrosymmetric 2,4,6-trinitrotoluene (TNT). These compounds exhibit variation in the refractive indices and absorption between 0.1 and 2.2 THz range. The DFT studies at the molecular and single-crystal level (using plane wave pseudo potential method) endorse in detecting these bands (with ∼1% deviation). The calculated vibrational frequencies and linear optical properties are found to have good agreement with the experimental data in UV-visible and THz regions.