Theoretical Study on the High Energy Density Compound Hexanitrohexaazatricyclotetradecanedifuroxan

Abstract

Density functional theory (DFT) has been employed to study the molecular geometries, electronic structures, infrared (IR) spectra, and thermodynamic properties of the high energy density compound hexanitrohexaazatricyclotetradecanedifuroxan (HHTTD) at the B3LYP/6-31G** level of theory. The calculated results show that there are four conformational isomers (α, β, γ and δ) for HHTTD, and the relative stabilities of four conformers were assessed based on the calculated total energies and the energy-gaps between the frontier molecular orbitals. The computed harmonic vibrational frequencies are in reasonable agreement with the available experimental data. Thermodynamic properties derived from the IR spectra on the basis of statistical thermodynamic principles are linearly correlated with the temperature. Detonation performances were evaluated by using the Kamlet-Jacobs equations based on the calculated densities and heats of formation. It was found that four HHTTD isomers with the predicted densities of ca. 2 g•cm -3 , detonation velocities near 10 km•s -1 , and detonation pressures over 45 GPa, may be novel potential candidates of high energy density materials (HEDM). These results may provide basic information for the molecular design of HEDM.

Quantum chemical study on 5-nitro-2,4-dihydro-3H-1,2,4-triazol-3-one (NTO) and some of its constitutional isomers

“…The molar volume was defined as inside a contour of 0.001 electrons/Bohr 3 density that was evaluated using a Monte Carlo integration implemented in the Gaussian 98 program. This method has been successfully tested on various CHNO molecules and accurately predicts the explosive properties [66][67][68][69][70][71]. In this study, single-point molecular volume calculations at B3LYP/6-311G(d,p) performed based on the B3LYP/6-31G(d,p) geometry optimized structures.…”

Molecular design of new nitramine explosives: 1,3,5,7-tetranitro-8-(nitromethyl)-4-imidazolino[4,5-b]4-imidazolino-[4,5-e] pyridine and its N-oxide

“…Table 3 collects the predicted ρ, D, and P of the title compounds. For comparison, the calculated and experimental results of the famous explosives HMX [51] and CL-20 [52] are also listed. From Fig.…”

“…4 and the detonation parameters evaluated using ρ p . Those in the brackets are the experimental values taken from Ref [51]. and[52] …”

Theoretical Studies on the Infrared Vibrational Spectra, Thermodynamic Properties and Nuclear Magnetic Resonance Spectra for Polynitro‐1,3‐bishomopentaprismanes

“…However, at the higher temperature, the vibrational movement is intensified, which therefore makes more contributions to the thermodynamic properties, resulting in the increase in the thermodynamic functions. Taking 2,5,6,9,11 23 ,12 25 -PNBPP as an example, the relationships between the thermodynamic functions and the temperature in the range 200-800 K can be expressed as in Figure 3a. It is obvious that, when the temperature goes up, the increments decrease for both (See Figure 1a for the atomic numbering).…”

“…On the other hand, there is unmatched progress in the computational modeling of IR and NMR parameters, especially by DFT methods. [7][8][9][10][11] In the present paper, the IR spectra, 13 C and 1 H NMR chemical shifts for a series of PNBPP derivatives were investigated by using DFT-B3LYP/6-31G* calculation. We hope that the computed vibrational frequencies and NMR chemical shifts of 13 C and 1 H atoms can provide references for experimentalists.…”