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1063969 
Journal Article 
Reaction of acetaldehyde with zirconium: A density functional theoretical study 
Dai, GL; Wang, CF; Wu, JY; Zhong, AG 
2011 
1 
Computational and Theoretical Chemistry
ISSN: 2210-271X
EISSN: 2210-2728 
965 
1 
60-67 
WOS:000289496300009 
The reaction mechanism of the Zr atom with CH(3)CHO has been investigated with a DFT approach. All the stationary points are determined at the UB3LYP/ECP/6-311++G** level of the theory. Both ground and excited state potential energy surfaces are investigated in detail. The present results show that the title reaction start with the formation of a eta(2)-CH(3)CHO-metal complex followed by C-C, aldehyde C-H, methyl C-H and C-O activation. These reactions can lead to six different products (HZrCH(3) + CO, ZrCO + CH(4), ZrCH(2)CO + H(2), ZrCOCH(3) + H, ZrCH(2)CHO + H and ZrO + C(2)H(4)). The minimum energy reaction path is found to involve the spin inversion in the initial reaction step. This potential energy curve-crossing dramatically affects reaction exothermic. As the triplet intermediates, transition states and products involved in the reaction lie below the ground reactants (Zr((5)F) + CH(3)CHO), the reaction is expected to occur spontaneously over the triplet potential energy surface. The present results may be helpful in understanding the mechanism of the title reaction and further experimental investigation of the reaction. (C) 2011 Elsevier B.V. All rights reserved. 
Theoretical chemistry; Density functional calculations; Potential energy surfaces; Zirconium; Acetaldehyde