Theoretical study of the reaction of V+ with SCO in gas phase

In order to elucidate the mechanism of reaction M+ + SCO, the reaction of V+ + SCO has been investigated using density functional theory (DFT) with the popular hybrid functional, B3LYP, in conjunction with 6-311+G* basis set both on the quintet and triplet potential energy surfaces (PESs). The crossing points (CPs) of the different potential energy surface (PESs) have been localized with the approach suggested by Yoshizawa et al. (K. Yoshizawa, Y. Shiota, T. Yamabe, J. Chem. Phys. 111 (1999) 538). The involving potential energy curve-crossing dramatically affects reaction mechanism. The present results show that the reaction mechanism is insertion-elimination mechanism both along the C-S and C-O bond activation branches, but the C-S bond activation is much more favorable than the C-O bond activation in energy. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction. (c) 2006 Elsevier B.V. All rights reserved.