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Interaction of Mo(CO) 6 and its derivative fragments with the Cu(001) surface: Influence on the decomposition process
Author(s) -
Dupont Céline,
Wan Xiaowen,
Petukhov Mikhail,
Krüger Peter
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.24744
Subject(s) - endothermic process , dissociation (chemistry) , chemistry , adsorption , molybdenum , exothermic reaction , density functional theory , decomposition , molecule , desorption , van der waals force , computational chemistry , inorganic chemistry , organic chemistry
A theoretical study on the adsorption and decomposition of molybdenum carbonyl on the copper (001) surface is reported. The adsorption structures and energies of Mo(CO) n molecules ( n = 1 … 6) are computed systematically using density functional theory with Van der Waals corrections. By analyzing the energies of the various conformations, the main factors that determine the stable adsorption geometry are identified. Insight into the thermodynamics of decomposition is gained by calculating the reaction energy for dissociation of Mo(CO) n into Mo(CO) n −1 and CO. In the gas phase, this reaction is highly endothermic for all n . On the Cu surface, however, removal of the first CO group ( n = 6) becomes strongly exothermic. The subsequent dissociation steps ( n < 6), are endothermic even on the surface, but the reaction energies are much reduced. Dissociation is found energetically more favorable than desorption in all cases. The results clearly show that molybdenum carbonyl decomposition is strongly facilitated by the presence of the Cu surface. © 2014 Wiley Periodicals, Inc.