Theoretical survey of the potential energy surface of Zr plus acetone reaction

The gas-phase reaction of zirconium atom with acetone is investigated using density functional theory. Geometries and energies of the reactants, intermediates, and products involved are calculated. 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 an O-attached complex (IM0). All possible pathways starting with C-O, C-H, and C-C activation are searched. These reactions can lead to four different products ((ZrO)-Zr-3 + C3H6, (ZrCH2COCH3)-Zr-2 + H-2, (ZrCH2)-Zr-3 + CH3CHO and (ZrCOCH2)-Zr-3 + CH4). The minimum energy reaction path is found to involve the spin inversion in the initial reaction step, and 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(F-5)+ CH3COCH3) after IM1 formation, 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.