论文部分内容阅读
用从头算分子轨道法对H与ClF生成HF反应的势能面进行了系统的计算 .优选了与生成HF有关的各种可能的过渡态 .通过从以F原子为中心的线状过渡态出发作IRC的计算 ,并结合偏离线状构型后势能面的扫描数据确定了生成HF的直接型反应途径 ;通过从以H原子为中心的过渡态出发作IRC的计算确定了生成HF的迁移型反应途径 .从理论上证实了Polanyi提出的关于H与ClF生成HF的反应过程包含直接型与迁移型两种机理的假设 .
The ab initio molecular orbital method was used to calculate the potential energy surface of HF reaction between H and ClF, and the possible transition states related to the formation of HF were optimized.From the linear transition state centered on F atom IRC calculation, and combined with the scan data of the potential energy surface deviating from the linear configuration, the direct reaction pathway for the generation of HF was confirmed. The calculation of IRC from the H atom-centered transition state confirmed the migration reaction of HF This paper theoretically confirms the hypothesis made by Polanyi that both the direct mechanism and the migratory mechanism are involved in the reaction process of HF with ClF.