Theoretical kinetic study on the decomposition of 1,5-diaminotetrazole

• Published in: Journal of physical organic chemistry 2015-06, Vol.28 (6), p.423-427
• Main Authors: He, Piao, Zhang, Jian-Guo, Feng, Li-Na, Wang, Kun, Zhang, Tong-Lai, Zhang, Shao-Wen
• Format: Article
• Language: English
• Subjects: 1,5‐daminotetrazole (DAT); 5-daminotetrazole (DAT); decomposition pathway; kinetics; rate constant
• ISSN: 0894-3230; 1099-1395
• DOI: 10.1002/poc.3428

1,5‐Daminotetrazole (DAT) is of much interest because of the practical significance and the diversity of characteristics. The study on the decomposition pathway and the kinetics of DAT has been performed based on the quantum chemistry theory. The minimum energy path (MEP) calculation has shown that NH2N3 and NH2CN are the initially detected products of DAT. And the structures of reactant, products and transition state were optimized with MP2 methods using 6‐311G** basis sets, and the energies were refined using CCSD(T)/6‐311G** levels of theory. The calculated rate constants were obtained using the conventional transition‐state theory (TST) and the canonical variational transition‐state theory (CVT) methods. The calculation results indicated that the energy barrier of decomposition reaction is 47.98 kcal mol−1 and the variational effect is small. In addition, the rate constants and the Arrhenius experience formula of DAT decomposition have been obtained between 200 and 2500 K temperature regions. The fitted three‐parameter expressions calculated using the TST and CVT methods are kT=1.27×10‐26×T3.60×e−8.07×103/Ts‐1 (TST) and kT=9.78×1011×T0.88×e−2.51×104/Ts‐1 (CVT). This work may provide the theoretical support for further experimental synthesis and testing. Copyright © 2015 John Wiley & Sons, Ltd. The study on the decomposition pathway and the kinetics of 1,5‐daminotetrazole (DAT) has been performed based on the quantum chemistry theory. And the structures of reactant, products, and transition state were optimized with MP2 methods using 6‐311G** basis sets, and the energies were refined using CCSD(T)/6‐311G** levels of theory. The calculated rate constants were obtained using the conventional transition‐state theory (TST) and the canonical variational transition‐state theory (CVT) methods.