A DFT study of the unimolecular decomposition of 1,2,4-butanetriol trinitrate

摘要

To improve understanding of the unimolecular decomposition mechanism of 1,2,4-butanetriol trinitrate (BTTN) in the gas phase, density functional theory calculations were performed to determine various decomposition pathways at the B3LYP/6-311G~(**) level. Two main mechanisms for the unimolecular decomposition of BTTN were found. In the first, homolysis of one of the O–NO_2 bonds occurs to form?NO_2 and CH_2ONO_2CHONO_2CH_2CH_2O?, which subsequently decomposes to form CH_3CHO + ?CHO + 3NO_2 + HCHO. In the second, successive HONO elimination reactions yield three HONO and OHCCH_2CHONO_2CH_2ONO_2 fragments, which subsequently decompose to form CH_3CHO + 2CO + 3HONO. We also found that the first pathway has a slightly lower activation energy than the second. The results show that the pathway involving O–NO_2 cleavage is slightly more energetically favorable than that involving HONO elimination.