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Pyridine adsorption on small Ni n ‐cluster ( n = 2,3,4): A study of geometry and electronic structure
Author(s) -
Ghatee Mohammad Hadi,
Pakdel Leila
Publication year - 2012
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.24358
Subject(s) - unpaired electron , cluster (spacecraft) , chemistry , adsorption , bond length , electronic structure , crystallography , pyridine , ground state , metal , basis set , atomic physics , computational chemistry , density functional theory , molecule , physics , crystal structure , organic chemistry , computer science , programming language
Adsorption of pyridine on Ni n ‐clusters (with n = 2,3,4) is studied by quantum chemical calculations at B3LYP/LANL2DZ and B3LYP/6‐311G ** levels. First, Ni n ‐clusters are investigated for accessible structure and electronic states. The lowest electronic state with four unpaired electrons is predicted for Ni 4 ‐cluster based on geometry and electronic structure, showing that the cluster stability nicely depends on number of unpaired electrons. Correction for basis set superposition error of metal‐metal bond is appreciable and has increasing effect on cluster binding energy. Next, adsorption of pyridine in planar and vertical adsorption modes is investigated on rhombus Ni 4 ‐cluster. The vertical mode is found (at B3LYP/6‐311G ** level) as the most favorable adsorption mode. Adsorption energy (Δ E ads ) depends on cluster size; adsorption on Ni 4 ‐cluster is most favorable with Δ E ads = −207.33 kJ/mol. The natural bond orbital analysis reveals the charge transfer in adsorbate/metal‐cluster. Results of investigations for the Ni 2 ‐ and Ni 3 ‐cluster are also presented. © 2012 Wiley Periodicals, Inc.