Wen-mei Wei, Ren-hui Zheng, Yan Tian, Tian-jing He, Li He, Dong-ming Chen, Fan-chen Liu. Theoretical Study of Isomerization and Decomposition Reactions for Methyl-nitramine[J]. Chinese Journal of Chemical Physics , 2007, 20(2): 126-134. doi: 10.1360/cjcp2007.20(2).126.9
Citation: Wen-mei Wei, Ren-hui Zheng, Yan Tian, Tian-jing He, Li He, Dong-ming Chen, Fan-chen Liu. Theoretical Study of Isomerization and Decomposition Reactions for Methyl-nitramine[J]. Chinese Journal of Chemical Physics , 2007, 20(2): 126-134. doi: 10.1360/cjcp2007.20(2).126.9

Theoretical Study of Isomerization and Decomposition Reactions for Methyl-nitramine

doi: 10.1360/cjcp2007.20(2).126.9
Funds:  This work was supported by the National Natural Science Foundation of China (No.20473078).
  • Received Date: 2006-06-28
  • The complex potential energy surface and reaction mechanisms for the unimolecular isomerization and decomposition of methyl-nitramine (CH3NHNO2) were theoretically probed at the QCISD(T)/6-311+G*//B3LYP/6-311+G* level of theory. The results demonstrated that there are four low-lying energy channels: (i) the N{N bond fission pathway; (ii) a sequence of isomerization reactions via CH3NN(OH)O; (IS2a); (iii) the HONO elimination pathway; (iv) the isomerization and the dissociation reactions via CH3NHONO (IS3). The rate constants of each initial step (rate-determining step) for these channels were calculated using the canonical transition state theory. The Arrhenius expressions of the channels over the temperature range 298-2000 K are k6(T)=1014:8e-46:0=RT , k7(T)=1013:7e-42:1=RT , k8(T)=1013:6e-51:8=RT and k9(T)=1015:6e-54:3=RT s-1, respectively. The calculated overall rate constants is 6.9£10-4 at 543 K, which is in good agreement with the experimental data. Based on the analysis of the rate constants, the dominant pathway is the isomerization reaction to form CH3NN(OH)O at low temperatures, while the N{N bond fission and the isomerization reaction to produce CH3NHONO are expected to be competitive with the isomerization reaction to form CH3NN(OH)O at high temperatures.
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Theoretical Study of Isomerization and Decomposition Reactions for Methyl-nitramine

doi: 10.1360/cjcp2007.20(2).126.9
Funds:  This work was supported by the National Natural Science Foundation of China (No.20473078).

Abstract: The complex potential energy surface and reaction mechanisms for the unimolecular isomerization and decomposition of methyl-nitramine (CH3NHNO2) were theoretically probed at the QCISD(T)/6-311+G*//B3LYP/6-311+G* level of theory. The results demonstrated that there are four low-lying energy channels: (i) the N{N bond fission pathway; (ii) a sequence of isomerization reactions via CH3NN(OH)O; (IS2a); (iii) the HONO elimination pathway; (iv) the isomerization and the dissociation reactions via CH3NHONO (IS3). The rate constants of each initial step (rate-determining step) for these channels were calculated using the canonical transition state theory. The Arrhenius expressions of the channels over the temperature range 298-2000 K are k6(T)=1014:8e-46:0=RT , k7(T)=1013:7e-42:1=RT , k8(T)=1013:6e-51:8=RT and k9(T)=1015:6e-54:3=RT s-1, respectively. The calculated overall rate constants is 6.9£10-4 at 543 K, which is in good agreement with the experimental data. Based on the analysis of the rate constants, the dominant pathway is the isomerization reaction to form CH3NN(OH)O at low temperatures, while the N{N bond fission and the isomerization reaction to produce CH3NHONO are expected to be competitive with the isomerization reaction to form CH3NN(OH)O at high temperatures.

Wen-mei Wei, Ren-hui Zheng, Yan Tian, Tian-jing He, Li He, Dong-ming Chen, Fan-chen Liu. Theoretical Study of Isomerization and Decomposition Reactions for Methyl-nitramine[J]. Chinese Journal of Chemical Physics , 2007, 20(2): 126-134. doi: 10.1360/cjcp2007.20(2).126.9
Citation: Wen-mei Wei, Ren-hui Zheng, Yan Tian, Tian-jing He, Li He, Dong-ming Chen, Fan-chen Liu. Theoretical Study of Isomerization and Decomposition Reactions for Methyl-nitramine[J]. Chinese Journal of Chemical Physics , 2007, 20(2): 126-134. doi: 10.1360/cjcp2007.20(2).126.9

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