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Density functional theory study of p ‐chloroaniline adsorption on Pd surfaces and clusters
Author(s) -
He Xiaobo,
Lyu Jinghui,
Zhou Hu,
Zhuang Guilin,
Zhong Xing,
Wang JianGuo,
Li Xiaonian
Publication year - 2014
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.24681
Subject(s) - adsorption , icosahedral symmetry , catalysis , density functional theory , chemistry , transition metal , benzene , molecule , palladium , cluster (spacecraft) , metal , crystallography , molecular orbital , octahedron , computational chemistry , organic chemistry , crystal structure , computer science , programming language
The adsorption mode of aromatic molecules on transition metal surfaces plays a key role in their catalytic transformation. In this study, by means of density functional theory calculations, we systematically investigate the adsorption of p ‐chloroaniline on a series of Pd surfaces, including stepped surfaces, flat surfaces, and clusters. The adsorption energies of p ‐chloroaniline on these substrates [Pd(221), Pd(211), Pd(111), Pd(100), Pd 13 ‐icosahedral, Pd 13 ‐cubo‐octahedron, Pd 55 ] are −1.90, −2.13, −1.70, −2.11, −2.53, −2.65, −2.23 eV, respectively. Benzene ring is adsorpted on catalyst rather than amine group in p ‐chloroaniline molecular. A very good linear relationship is further found between the adsorption energies of p ‐chloroaniline and the d ‐band center of both Pd surfaces and clusters. The lower of d ‐band center of Pd models, the stronger adsorption of p ‐chloroaniline on catalysts. In addition, the frontier molecular orbital and density of states analysis explain the adsorption energy sequence: cluster Pd 13 > stepped Pd(221) surface > flat Pd(111) surface. © 2014 Wiley Periodicals, Inc.