5-硝基-1-氢-四唑分子热分解反应机理的密度泛函理论研究 |
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引用本文: | 汪敬,顾健德,田安民. 5-硝基-1-氢-四唑分子热分解反应机理的密度泛函理论研究[J]. 化学学报, 2002, 60(4): 590-595 |
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作者姓名: | 汪敬 顾健德 田安民 |
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作者单位: | 1. 四川大学化学学院,成都,610064 2. 中国科学院上海药物研究所,上海,200031 |
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基金项目: | 国家自然科学基金 (No .2 98730 2 9)资助项目 |
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摘 要: | 利用密度泛函理论研究了5-硝基-1-氢-四唑分子热分解的反应机理。首先用 B3LYP/6-31G(d)方法优化反应中反应物、过渡态、中间体以及产物的几何构型, 通过振动分析得到零点能校正值并确认反应的过渡态。此外,对各个构型作了 CCSD(T)/6-31G(d,p)水平下的单点计算。报道了三条可能的反应途径,即直接 开环途径和质子转移途径;其中N(1)-N(2)键断裂直接开环的机理与文献报道 一致;而涉及质子转移的反应途径则是一个新的发现;另一条关于N(4)-C(5) 键断裂直接开环的途径由于能垒较高,因此发生的几率较小。
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关 键 词: | 硝基化合物 四唑 P 热分解 过渡态理论 构型 |
修稿时间: | 2001-07-10 |
The Mechanisms of Thermal Decomposition of 5-Nitro-1- hydrogentetrazole: A Density Function Theory Study |
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Affiliation: | Department of Chemistry, Sichuan University, Chengdu(610064);Shanghai Institute of Materia Medica, Shanghai Institute for Biological Sciences, Chinese Academy of Sciences.Shanghai(200031) |
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Abstract: | The mechanisms dealing with the thermal decomposition of 5-nitro-1-hydrogen-tetrazole are studied by density function theory. The geometries of the reactants, transition states, intermediates and products are optimized at the B3LYP/6-31G(d) level. The corresponding vibrational frequencies are calculated to take account of the zero-point vibrational energy (ZPE) and to identify the transition structures. The single point calculations are obtained at the CCSD(T)/6-31G(d, p) level. Three possible reaction channels are shown, including direct ring rupture channels and proton transfer channel. The one of N(1)-N(2) bond-breaking ring rupture channel agrees with the result reported before. The one dealing with proton transfer shows a new feature of the titled compound's thermal decomposition. The other one of N(4)-C(5) bond-breaking ring rupture has the highest activation barrier of all the three channels and therefore it occurs less often than the former two. |
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Keywords: | nitro-1-hydrogen-tetrazole density function theory (DFT) thermal decomposition |
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