Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101

4-amino-7,8-dinitropyrazolo-[5,1-d][1,2,3,5]-tetrazine 2-oxide (BITE-101) outperforms the benchmark explosive HMX in all aspects, showing application prospects as a new generation of high energy density material. To obtain the thermal decomposition mechanism and key intermediates of BITE-101, the in...

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Main Authors: Zi-xuan Yang, Shuang-fei Zhu, Hai Duan, Rui-jun Gou, Yang Liu, Shu-hai Zhang
Format: Article
Language:English
Published: KeAi Communications Co. Ltd. 2025-03-01
Series:Energetic Materials Frontiers
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666647225000041
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author Zi-xuan Yang
Shuang-fei Zhu
Hai Duan
Rui-jun Gou
Yang Liu
Shu-hai Zhang
author_facet Zi-xuan Yang
Shuang-fei Zhu
Hai Duan
Rui-jun Gou
Yang Liu
Shu-hai Zhang
author_sort Zi-xuan Yang
collection DOAJ
description 4-amino-7,8-dinitropyrazolo-[5,1-d][1,2,3,5]-tetrazine 2-oxide (BITE-101) outperforms the benchmark explosive HMX in all aspects, showing application prospects as a new generation of high energy density material. To obtain the thermal decomposition mechanism and key intermediates of BITE-101, the initial decay pathways were studied by using the M062X method for optimization and DLPNO-CCSD(T)/cc-pVTZ methods for energies. The energy barrier results showed that the nitro-nitrite isomerization was the lowest, indicating that this path was the most advantageous in the reaction of BITE-101. In addition, the H transfer reaction has a promoting effect on the ring-opening reaction. Additionally, the influence of functional group position on the initial decomposition mechanism of energetic materials is also discussed. The results show that the most likely first decay paths are all caused by the functional groups on the tetrazine ring, and the position of the amino group had a great influence on the ring-opening reaction. These reactions can be clearly seen from the changes in ELF and Mayer bond order. These results will certainly deepen our understanding of the decay mechanism of pyrazolo-tetrazine.
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issn 2666-6472
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publishDate 2025-03-01
publisher KeAi Communications Co. Ltd.
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series Energetic Materials Frontiers
spelling doaj-art-bfa20f3083494a068235ee12c95e879e2025-08-20T02:26:40ZengKeAi Communications Co. Ltd.Energetic Materials Frontiers2666-64722025-03-0161425010.1016/j.enmf.2025.01.004Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101Zi-xuan Yang0Shuang-fei Zhu1Hai Duan2Rui-jun Gou3Yang Liu4Shu-hai Zhang5School of Environment and Safety Engineering, North University of China, Taiyuan, 030051, ChinaSchool of Environment and Safety Engineering, North University of China, Taiyuan, 030051, China; Corresponding author.Shaanxi Qinghua Vehicle Safety Systems Co.,Ltd, ChinaSchool of Environment and Safety Engineering, North University of China, Taiyuan, 030051, ChinaSchool of Environment and Safety Engineering, North University of China, Taiyuan, 030051, ChinaSchool of Environment and Safety Engineering, North University of China, Taiyuan, 030051, China; Corresponding author.4-amino-7,8-dinitropyrazolo-[5,1-d][1,2,3,5]-tetrazine 2-oxide (BITE-101) outperforms the benchmark explosive HMX in all aspects, showing application prospects as a new generation of high energy density material. To obtain the thermal decomposition mechanism and key intermediates of BITE-101, the initial decay pathways were studied by using the M062X method for optimization and DLPNO-CCSD(T)/cc-pVTZ methods for energies. The energy barrier results showed that the nitro-nitrite isomerization was the lowest, indicating that this path was the most advantageous in the reaction of BITE-101. In addition, the H transfer reaction has a promoting effect on the ring-opening reaction. Additionally, the influence of functional group position on the initial decomposition mechanism of energetic materials is also discussed. The results show that the most likely first decay paths are all caused by the functional groups on the tetrazine ring, and the position of the amino group had a great influence on the ring-opening reaction. These reactions can be clearly seen from the changes in ELF and Mayer bond order. These results will certainly deepen our understanding of the decay mechanism of pyrazolo-tetrazine.http://www.sciencedirect.com/science/article/pii/S2666647225000041Quantum chemistryPyrazolo-tetrazineDecomposition mechanismKey intermediatesFunctional groups
spellingShingle Zi-xuan Yang
Shuang-fei Zhu
Hai Duan
Rui-jun Gou
Yang Liu
Shu-hai Zhang
Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101
Energetic Materials Frontiers
Quantum chemistry
Pyrazolo-tetrazine
Decomposition mechanism
Key intermediates
Functional groups
title Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101
title_full Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101
title_fullStr Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101
title_full_unstemmed Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101
title_short Quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo-tetrazine: A case study of BITE-101
title_sort quantum chemistry modeling of the unimolecular decomposition mechanism and substituent effects of pyrazolo tetrazine a case study of bite 101
topic Quantum chemistry
Pyrazolo-tetrazine
Decomposition mechanism
Key intermediates
Functional groups
url http://www.sciencedirect.com/science/article/pii/S2666647225000041
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