Nascent state distributions of NO(X 2Π) generated from the reaction of S(1D) with N2O: Intramolecular vibrational-energy redistribution in the reaction intermediate
Nascent state distributions of NO(X 2Π) generated from the reaction of S(1D) with N2O: Intramolecular vibrational-energy redistribution in the reaction intermediate
复制标题
S(1D) 与 N2O 反应生成的 NO(X 2Π) 的初生态分布：反应中间体中的分子内振动能量重新分布
DOI：
10.1063/1.478629
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发表时间：
1999
期刊：
影响因子：
--
通讯作者：
O. Kajimoto
中科院分区：
文献类型：
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作者：
H. Akagi;Y. Fujimura;O. Kajimoto
利用激光诱导荧光（LIF）技术测定了S(1D)+N2O→NO+NS反应生成的NO（X 2Π）的初生内态分布。NO的平均振动能相对于统计期望值为37%。该量明显小于同价反应18O(1D)+N2 16O→N 18O+N 16O的片段N 16O的量，但仍大于16O(1D)+H2 18O反应产生的18OH的量。为了解释所观察到的产物能量分配的差异，我们将量子分子内振动能量重分配（IVR）表示应用于碰撞复合体中的能量混合。利用具有动量耦合的局部模振动模型，我们提取了这些反应中决定能量分配的关键因素。仅由大质量原子组成的反应体系通常具有大的振动耦合和大的态密度，这两者都有利于快速反应。
The nascent internal state distribution of NO(X 2Π) generated from the reaction, S(1D)+N2O→NO+NS, has been determined by utilizing the laser-induced fluorescence (LIF) technique. The average vibrational energy of NO relative to the statistically expected value is found to be 37%. This amount is obviously smaller than that of the fragment N 16O of the isovalent reaction 18O(1D)+N2 16O→N 18O+N 16O, though it is still larger than that of 18OH produced from the 16O(1D)+H2 18O reaction. To interpret the observed difference in the product energy partitioning, we have applied the quantal intramolecular vibrational-energy redistribution (IVR) representation to the energy mixing in the collision complex. Using a local-mode vibration model with momentum couplings, we have extracted the crucial factors determining the energy partitioning in these reactions. The reaction system consisting of only heavy mass atoms generally has a large vibrational coupling and a large density of states, both of which favor the rapid e...