Reaction mechanism of the CCN radical with nitric oxide
Reaction mechanism of the CCN radical with nitric oxide
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DOI：
10.1002/jcc.20396
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发表时间：
2006-05
影响因子：
3
通讯作者：
Lin Jin;Yi‐hong Ding;Jian Wang;Chia-Chung Sun
中科院分区：
文献类型：
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作者：
Lin Jin;Yi‐hong Ding;Jian Wang;Chia-Chung Sun
为了研究碳自由基CCN去除一氧化氮的可能性，通过构建单线态和三重态[C2N2O]势能面（PESs），在高斯‐3//B3LYP/6‐31G(d)水平上对CCN + NO反应进行了详细的计算研究。链状异构体NCCNO（单线态- 106.5，三联体顺式- 48.2和三联体反式- 47.6 kcal/mol）的无障碍形成是单线态和三联体PESs最有利的入口攻击。随后，单线态NCCNO发生O -转移，形成支链中间单线态NCC(O)N(- 85.6)，通过中间单线态NCOCN（- 120.3）生成片段CN + NCO（- 51.2）。三重态NCCNO的简单演化是直接N-O断裂形成弱结合的复合三重态NCCN…O(- 56.2)，然后最终破碎成NCCN + 30o（- 53.5）。然而，3CNN + CO（- 105.6）和3CNN + CO（- 74.6）在动力学上的竞争力要弱得多。生成CN + NCO和NCCN + 30o所涉及的过渡态都远低于反应物。因此，新型反应CCN + NO即使在低温下也能有效地进行，并有望在燃烧和星际过程中发挥作用。CCN + NO和CH + NO反应机制在单重态PES上存在显著差异。©2006 Wiley期刊公司[J] .计算机工程学报，2006,31 (2):389 - 393
To investigate the possibility of the carbyne radical CCN in removal of nitric oxide, a detailed computational study is performed at the Gaussian‐3//B3LYP/6‐31G(d) level on the CCN + NO reaction by constructing the singlet and triplet electronic state [C2N2O] potential energy surfaces (PESs). The barrierless formation of the chain‐like isomers NCCNO (singlet at −106.5, triplet cis at −48.2 and triplet trans at −47.6 kcal/mol) is the most favorable entrance attack on both singlet and triplet PESs. Subsequently, the singlet NCCNO takes an O‐transfer to form the branched intermediate singlet NCC(O)N (−85.6), which can lead to the fragments CN + NCO (−51.2) via the intermediate singlet NCOCN (−120.3). The simpler evolution of the triplet NCCNO is the direct N–O rupture to form the weakly bound complex triplet NCCN…O (−56.2) before the final fragmentation to NCCN + 3O (−53.5). However, the lower lying products 3NCN + CO (−105.6) and 3CNN + CO (−74.6) are kinetically much less competitive. All the involved transition states for generation of CN + NCO and NCCN + 3O lie much lower than the reactants. Thus, the novel reaction CCN + NO can proceed effectively even at low temperatures and is expected to play a role in both combustion and interstellar processes. Significant differences are found on the singlet PES between the CCN + NO and CH + NO reaction mechanisms. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 883–893, 2006