A Theoretical Study of the CH2N System: Reactions in both Lowest Lying Doublet and Quartet States
A Theoretical Study of the CH2N System: Reactions in both Lowest Lying Doublet and Quartet States
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CH2N体系的理论研究：最低双态和四重态反应
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
M. Nguyen
中科院分区：
文献类型：
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作者：
R. Sumathi;M. Nguyen
在6-311++G（d，p）和6-311 ++G（3df，3dp）基组下，采用二阶微扰理论（UMP 2）和CCSD（T）方法，对[CH 2 N]体系中H2+CN，H+HCN，和H+HNC在最低的双电子态和四电子态。势垒高度、振动波数和惯性矩随后用于使用量子Rice−Ramsperger−卡塞尔（QRRK）理论计算速率常数。在300 K时，H+HCN反应的总速率常数k∞为2.2 × 107 cm ~ 3 mol ~（-1）s ~（-1），表明反应是缓慢的，主要与加合物的稳定化有关。另一方面，H+HNC反应被计算为压力无关的快速反应，速率系数为1.9 × 1011 cm ~ 3 mol ~（-1）s ~（-1），主要导致H+HCN解离产物。看台...
Ab initio molecular orbital calculations at the second-order perturbation theory (UMP2) and coupled cluster singles and doubles with corrected triples (CCSD(T)) levels with 6-311++G(d,p) and 6-311++G(3df,3dp) basis sets have been carried out to construct the potential energy surfaces related to the various reactions of the [CH2N] system, including H2+CN, H+HCN, and H+HNC in both lowest lying doublet and quartet electronic states. Barrier heights, vibrational wavenumbers, and moments of inertia were then utilized in the calculations of rate constants using a quantum Rice−Ramsperger−Kassel (QRRK) theory. The calculated total rate constant k∞ for the H+HCN reaction at 300 K is 2.2 × 107 cm3 mol-1 s-1 and is suggestive of a slow reaction and it corresponds predominantly to the stabilization of the adducts. On the other hand, the H+HNC reaction is calculated to be a pressure-independent fast reaction with a rate coefficient of 1.9 × 1011 cm3 mol-1 s-1 leading primarily to H+HCN dissociation products. The stand...