构造方法及几个简例PartialPotentialEnergySurfaceand-Eduwest.PDF

2005 年第63 卷 化 学 学 报 Vol. 63, 2005 第5 期, 372～376 ACTA CHIMICA SINICA No. 5, 372～376 ·研究论文· 偏分势能面及其应用(I): 概念、构造方法及几个简例 孙孝敏a 王华阳a 蔡政亭*,a 冯大诚a 边文生b (a 山东大学理论化学研究所 济南 250100) (b 中国科学院化学研究所分子反应动力学国家重点实验室 北京 100080) 摘要 提出了偏分势能面的概念, 偏分势能面可由完全势能面抽取出来, 也可采用 ab initio 方法进行构造. 作为范例, 给出了F ＋H →FH ＋H, H ＋H →H ＋H, I ＋HI→IH ＋I 及Na ＋I →Na＋＋I－ 等体系中几种偏分势能面的构造和应用. 2 2 2 2 2 可以看到, 应用偏分势能面对于分析反应机理及散射共振态的生成方面显示突出优点. 关键词 势能面; 偏分势能面; 反应路径; 动力学Eyring 湖; 散射共振态 Partial Potential Energy Surface and Its Applications (I): Conception, Method of Construction and Several Examples SUN, Xiao-Mina WANG, Hua-Yanga CAI, Zheng-Ting*,a FENG, Da-Chenga BIAN, Wen-Shengb a ( Institute of Theoretical Chemistry, Shangdong University, Jinan 250100) (b State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080) Abstract The conception of partial potential energy surface (PPES) was presented in this paper. PPES can be extracted from complete potential energy surface (CPES), otherwise, it can be constructed with ab initio method. For the systems of F ＋H →FH ＋H, H ＋H →H ＋H, I ＋HI→IH ＋I and Na ＋I →Na＋＋I－, the 2