物理化学学报 >> 2015, Vol. 31 >> Issue (11): 20772077-2082.doi: 10.3866/PKU.WHXB201509143

理论与计算化学 上一篇    下一篇

应用多中心分区方法构建H3分子反应势能面

戴伟1,2,陈柳杨2,郑利敏2,杨明晖2()   

  1. 1 湖北第二师范学院物理与机电工程学院,武汉430205
    2 中国科学院武汉物理与数学研究所,武汉430071
  • 收稿日期:2015-07-06 发布日期:2015-11-13
  • 基金资助:
    国家留学基金委项目(201408420174);湖北省教育厅科学技术项目(Q20133005);湖北省自然科学基金(2014CFB428, 2015CFB502)

Application of the Multi-Center Partition Method to Construct the Potential Energy Surface of H3

Wei. DAI1,2,Liu-Yang. CHEN2,Li-Min. ZHENG2,Ming-Hui. YANG2()   

  1. 1 School of Physics and Mechanical & Electrical Engineering, Hubei University of Education, Wuhan 430205, P. R. China
    2 Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P. R. China
  • Received:2015-07-06 Published:2015-11-13
  • Supported by:
    the China Scholarship Council(201408420174);Science and Technology Research Program of the EducationDepartment, Hubei Province, China(Q20133005);Natural Science Foundation of Hubei Province, China(2014CFB428, 2015CFB502)

摘要:

势能面在分子反应动力学的研究中起着非常重要的作用.本文提出了一种新的势能面构建方法——多中心分区法.通过比较London-Eyring-Polanyi-Sato (LEPS)势能、多体展开势能、置换对称不变多项式三种方法,确定了H3分子的最佳势能函数表达形式,并应用准经典轨线方法分析了势能面的合理性,结果表明置换对称不变多项式能很好地描述H3分子的势能面特征.结合置换对称不变多项式和本文提出的多中心分区方法,可以有效改善H3分子势能面的精度并可能推广到高维反应势能面.

关键词: 势能面拟合, 准经典轨线法, 多中心分区

Abstract:

The potential energy surface plays an important role in studying molecular reaction dynamics. In this work, a new method, namely the "multi-center partition" method, is proposed to construct the potential energy surface of H3. The optimized function is first determined by comparing the London-Eyring-Polanyi-Sato (LEPS) potential, the many-body expansion potential, and the permutation-invariant polynomial potential. This comparison shows that the permutation-invariant polynomial fitting proposed by Bowman is the most efficient method for describing the topology of the H3 system. The quasi-classical trajectory method is used to analyze the rationality of those potential energy surfaces. By combining the multi-center partition method with the permutation-invariant polynomial method, the accuracy of the H3 molecular potential energy surface is greatly improved and could possibly be used in the fitting of potential energy surfaces in other systems.

Key words: Potential energy surface fitting, Quasi-classical trajectory method, Multi-center partition

MSC2000: 

  • O641.3