HNNC Radical and Its Role in the CH + N2 Reaction
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- 作者：Michael R. Berman ; Takashi Tsuchiya ; Adriana Gregu
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- 刊名：Journal of Physical Chemistry A
- 出版年：2007
- 出版时间：July 26, 2007
- 年：2007
- 卷：111
- 期：29
- 页码：6894 - 6899
- 全文大小：308K
- 年卷期：v.111,no.29(July 26, 2007)
- ISSN：1520-5215
文摘
A previously unreported channel in the spin-allowed reaction path for the CH + N2 reaction that involves theHNNC radical is presented. The structures and energetics of the HNNC radical and its isomers HCNN andHNCN and the relevant intermediates and transition states that are involved in the proposed mechanism areobtained at the coupled cluster singles and doubles level of theory with noniterative triples correction (CCSD(T)) using a converging series of basis sets aug-cc-pVDZ, aug-cc-pVTZ, and aug-cc-pVQZ. The aug-cc-pVQZ basis is used for all the final single point energy calculations using the CCSD(T)/aug-cc-pVTZ optimizedgeometries. We find the HNNC radical to have a heat of formation of 
fH0 (HNNC) = 116.5 kcal mol-1. Anassessment of the quality of computed data of the radical species HNCN and HCNN is presented by comparisonwith the available experimental data. We find that HNNC can convert to HNCN, the highest barrier in thispath being 14.5 kcal mol-1 above the energy of the CH + N2 reactants. Thus, HNNC can play a role in thehigh-temperature spin-allowed mechanism for the reaction of CH + N2 proposed by Moskaleva, Xia, andLin (Chem. Phys. Lett. 2000, 331, 269).
fH0 (HNNC) = 116.5 kcal mol-1. Anassessment of the quality of computed data of the radical species HNCN and HCNN is presented by comparisonwith the available experimental data. We find that HNNC can convert to HNCN, the highest barrier in thispath being 14.5 kcal mol-1 above the energy of the CH + N2 reactants. Thus, HNNC can play a role in thehigh-temperature spin-allowed mechanism for the reaction of CH + N2 proposed by Moskaleva, Xia, andLin (Chem. Phys. Lett. 2000, 331, 269).