物理化学学报 >> 2006, Vol. 22 >> Issue (05): 538-541.doi: 10.1016/S1872-1508(06)60019-3

研究论文 上一篇    下一篇

PdN、PdN2分子的结构与势能函数*

朱瑜;蒋刚;方芳;于桂凤;朱正和   

  1. 四川大学原子与分子物理研究所, 成都610065
  • 收稿日期:2005-10-19 修回日期:2005-11-06 发布日期:2006-04-28
  • 通讯作者: 蒋刚 E-mail:gjiang@scu.edu.cn

Structure and Potential Energy Function of PdN and PdN2 Molecules*

ZHU Yu;JIANG Gang;FANG Fang;YU Gui-Feng;ZHU Zheng-He   

  1. Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, P. R. China
  • Received:2005-10-19 Revised:2005-11-06 Published:2006-04-28
  • Contact: JIANG, Gang E-mail:gjiang@scu.edu.cn

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摘要： 在Pd 的RECP 近似下, 运用B3LYP 方法, 对Pd 采用基集合SDD, 对N 采用基集合AUG鄄cc鄄pVTZ, 对PdN 和PdN2分子的微观结构进行了理论计算. PdN 分子的基电子状态为4撞-, PdN2分子的最稳定构型为单重态的线性Pd—N—N(C肄V),其电子状态为1撞+. 采用最小二乘法拟合出PdN 分子的Murrell鄄Sorbie 势能函数, 使用多体展式理论导出了势函数中的参数, 进而给出PdN2分子基态势函数的解析表达式, 其势能面准确地复现了平衡稳态结构和能量关系, 表现了Pd 内迁移的详细过程, 存在一个C2V构型的鞍点(RNN=0.11700 nm, RPdN=0.22088 nm). 由图得到内迁移的能垒为0.5197 eV, 与计算值0.4560 eV 接近.

关键词: PdN, PdN2, 密度泛函, 相对论有效原子实势(RECP), 多体展式势能函数

Abstract: Based on the relativistic effective cores potential (RECP/SDD) for Pd atom and AUG-cc-pVTZ basisfunction for N atom, the structures of PdN and PdN2 have been optimized using B3LYP method. The results show thatthe ground state of PdN is 4[SIGMA]- and the ground state of PdN2 is C[infinity]V symmetry and 1[SIGMA]+ state. The Murrell-Sorbie potential energy function of PdN molecule has been fitted through the least square fitting, and the potential energy function of PdN2 is given by many-body expansion theory. The potential energy curves describe the structure character of PdN and PdN2 ground state molecules rightly, which details the inner transfer process of Pd. There is a saddle of C2V structure(RNN=0.11700 nm, RPdN=0.22088 nm). The energy barrier of inner transfer is 0.5197 eV, which is close to the calculated value of 0.4560 eV.

Key words: PdN, PdN2, Density functional method, Relativistic effective core potential(RECP), Many-body expansion potential energy function