TY - JOUR

T1 - A detailed chemical kinetic mechanism of 1,1-diamino-2,2-dinitroethylene (FOX-7) initial decomposition in the gas phase

AU - Lyu, Jie Yao

AU - Zhu, Qiren

AU - Bai, Xin

AU - Ren, Xuan

AU - Li, Jing

AU - Chen, Dongping

AU - Kiselev, Vitaly G.

AU - Li, Yang

AU - Yang, Wenming

N1 - We would like to express our sincere gratitude to the Dean's Chair fund at the National University of Singapore (WBS No. E-465-00-0010-02 ) and the High Performance Computing of NUS for their support. We also acknowledge the National Research Foundation (NRF) under the Prime Minister's Office, Singapore, for their support through the Campus for Research Excellence and Technological Enterprise (CREATE) Programme (A00053280300).

PY - 2023/9

Y1 - 2023/9

N2 - 1,1-Diamino-2,2-dinitroethylene (FOX-7 or DADNE) is a promising ingredient of the low-vulnerability propellants. However, one of the major concerns in its further development and applications is the lack of detailed kinetic mechanism for its initial decomposition in the gas phase. In this study, a detailed chemical kinetic mechanism consisting of 38 species and 131 reactions was developed to describe the initial decomposition process of FOX-7. At first, a comprehensive reaction network was established with the aid of reactive molecular dynamics (MD) simulation. Then, the potential energy surfaces (PES) for both unimolecular and bimolecular reactions were identified at the QCISD(T)/CBS//M062X/6-311++G(d,p) level of theory. The rate coefficients were obtained by solving RRKM/ME, and the thermochemical properties of relevant species were calculated at CBS-APNO/G3/G4 levels with the atomization method. Finally, these kinetic and thermochemistry data were processed into a kinetic mechanism and used to simulate the initial decomposition process of FOX-7. The results demonstrated that the H-atom transfer to the distant C-atom followed by the nitro elimination dominates the initial decomposition, and the reaction FOX-7 = R3a + NO2 becomes the most significant one under high temperatures (Channel C3). Besides, bimolecular reactions play a role as the decomposition goes on. Overall, this work provides quantitative predictions of the reaction pathways of gas-phase FOX-7 initial decomposition, and it would serve as a solid foundation for the development of a fully detailed combustion kinetic mechanism for FOX-7.

AB - 1,1-Diamino-2,2-dinitroethylene (FOX-7 or DADNE) is a promising ingredient of the low-vulnerability propellants. However, one of the major concerns in its further development and applications is the lack of detailed kinetic mechanism for its initial decomposition in the gas phase. In this study, a detailed chemical kinetic mechanism consisting of 38 species and 131 reactions was developed to describe the initial decomposition process of FOX-7. At first, a comprehensive reaction network was established with the aid of reactive molecular dynamics (MD) simulation. Then, the potential energy surfaces (PES) for both unimolecular and bimolecular reactions were identified at the QCISD(T)/CBS//M062X/6-311++G(d,p) level of theory. The rate coefficients were obtained by solving RRKM/ME, and the thermochemical properties of relevant species were calculated at CBS-APNO/G3/G4 levels with the atomization method. Finally, these kinetic and thermochemistry data were processed into a kinetic mechanism and used to simulate the initial decomposition process of FOX-7. The results demonstrated that the H-atom transfer to the distant C-atom followed by the nitro elimination dominates the initial decomposition, and the reaction FOX-7 = R3a + NO2 becomes the most significant one under high temperatures (Channel C3). Besides, bimolecular reactions play a role as the decomposition goes on. Overall, this work provides quantitative predictions of the reaction pathways of gas-phase FOX-7 initial decomposition, and it would serve as a solid foundation for the development of a fully detailed combustion kinetic mechanism for FOX-7.

KW - Decomposition

KW - FOX-7

KW - Kinetics

KW - Molecular dynamics

KW - Quantum chemical

KW - Thermochemistry

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85161324517&origin=inward&txGid=b4ebd10c6dd10b80b30b5a33bcd6db87

UR - https://www.mendeley.com/catalogue/8313c015-6233-3645-85dc-67a1ff1840ab/

U2 - 10.1016/j.combustflame.2023.112877

DO - 10.1016/j.combustflame.2023.112877

M3 - Article

VL - 255

JO - Combustion and Flame

JF - Combustion and Flame

SN - 0010-2180

M1 - 112877

ER -