化学学报 ›› 2004, Vol. 62 ›› Issue (18): 1775-1779. 上一篇    下一篇

研究论文

Pd6簇与H2分子相互作用的密度泛函理论研究

王延金1, 张敬来2, 曹泽星1, 张乾二1   

  1. 1. 厦门大学化学系固体表面物理化学国家重点实验室, 厦门, 361005;
    2. 河南大学化学系, 开封, 475001
  • 投稿日期:2003-11-25 修回日期:2004-02-11 发布日期:2014-02-17
  • 通讯作者: 曹泽星,E-mail:zxcao@xmu.edu.cn E-mail:zxcao@xmu.edu.cn
  • 基金资助:
    国家自然科学基金(Nos.20173042,20233020,20021002)资助项目.

Density Functional Theory Study on the Interaction of Pd6 with Multiple H2

WANG Yan-Jin1, ZHANG Jing-Lai2, CAO Ze-Xing1, ZHANG Qian-Er1   

  1. 1. Department of Chemistry, State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005;
    2. Department of Chemistry, Henan University, Kaifeng 475001
  • Received:2003-11-25 Revised:2004-02-11 Published:2014-02-17

通过相对论有效核势密度泛函理论计算,优化了Pa6(H)2和Pd6(H)4等簇的平衡几何结构,预测了氢分子在Pd6簇表面上的吸附行为与活化解离性质.计算结果表明,单态的Pd6簇可以活化两个氢分子;第一个H2和第二个H2吸附解离过程速率决定步骤的能垒分别是66.4和24.5 kJ/mol.在形成的分子氢配合物Pd6(H2)和Pd6(H)2H2中,H2主要作为给电子配体.在最稳定的二氢簇合物Pd6(H)2中,H倾向与3个Pd相互作用,形成面位氢的多核成键吸附方式.

关键词: Pd6和Pd6H4簇, 分子H2的吸附与解离, DFT/B3LYP计算

Equilibrium geometries of Pd6H2, Pd6(H)2 and Pd6(H)4 clusters and multiple H2 adsorption and dissociation on Pd6 were investigated by density functional theory calculations with the relativistic effective core potential. Present calculations show that barriers of the rate-determining steps for the first H2 and the second H2 activation processes are 66.4 and 24.5 kJ/mol, respectively. In the dihydrogen complexes the H2-ligand behaves as donor in the molecular bonding between H2 and Pd6. Chemisorbed hydrogen atoms prefer to bind the Pd3 facet of Pd6 in the most stable hydride complex Pd6(H)2.

Key words: Pd6 and Pd6H4 cluster, H2 adsorption and dissociation, DFT/B3L YP calculation