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在6-311G(d,p)基组水平上,采用全电子的UMP2方法对HNCO和CN自由基的反应途径进行了研究,结果表明,反应存在如下两条反应通道:HNCO+CN→NCO+HCN(1);HNCO+CN→HNCN+CO(2).其中反应(1)是吸氢反应,氢转移过程在分子间以协同方式进行,UMP2(full)/6-311G(d,p)计算位垒是20.80 kJ/mol,在反应的温度区间(1000-2100 K),传统过渡态理论得出的速率常数值范围是0.32×10-11,-6.9×10-11cm3·mol-1·S-1,支持了实验预测结果.反应(2)是分步反应,在反应途径上存在分子中间体,UMP2(full)/6-311G(d,p)计算位垒为83.42 kJ/mol.反应通道(2)的位垒大于反应通道(1).
At 6-311G (d, p) group level, all-electron UMP2 method was used to study the reaction pathway of HNCO and CN. The results showed that there are two reaction channels: HNCO + CN → NCO + HCN (1); HNCO + CN → HNCN + CO (2). The reaction (1) is a hydrogen absorption reaction and the hydrogen transfer process proceeds in a synergistic manner between molecules. UMP2 (full) / 6-311G The calculated barrier is 20.80 kJ / mol. The rate constants obtained by the traditional transition state theory range from 0.32 × 10-11 to -6.9 × 10-11 cm3 · mol-1 in the reaction temperature range (1000-2100 K) S-1, which supports the experimental predictions, reaction (2) is a staged reaction with molecular intermediates in the reaction pathway and the calculated barrier to UMP2 (full) / 6-311G (d, p) is 83.42 kJ / mol. The barrier of the reaction channel (2) is larger than the reaction channel (1).