Pd6簇与H2分子相互作用的密度泛函理论研究

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. 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. 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

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摘要/Abstract

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

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王延金, 张敬来, 曹泽星, 张乾二. Pd₆簇与H₂分子相互作用的密度泛函理论研究[J]. 化学学报, 2004, 62(18): 1775-1779.

WANG Yan-Jin, ZHANG Jing-Lai, CAO Ze-Xing, ZHANG Qian-Er. Density Functional Theory Study on the Interaction of Pd6 with Multiple H₂[J]. Acta Chimica Sinica, 2004, 62(18): 1775-1779.

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Pd₆簇与H₂分子相互作用的密度泛函理论研究

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

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