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Abstract: The gas-phase reactions of fluorocarbon compounds CH4– n F n (n =1–3) with Pt (3D, 1S) have been systematically explored via density functional theory (DFT) in order to investigate the mechanisms of these reactions. The results indicate that a reaction of CH3F with Pt (3D, 1S) experiences a rearrangement process to generate counterintuitive production (CH2F−PtH). CH2F2 and CHF3 activation by Pt (3D, 1S) yields high-oxidation-state complexes with carbon–metal double bonds. Moreover, the attack of platinum atoms on fluorine atoms in different fluorocarbon compounds involves intersystem crossing (ISC) between triplet and singlet state Potential Energy Surfaces (PESs). The crossing points (CPs) have been located by the intrinsic reaction coordinate (IRC) approach used by Yoshizawa et al. and corresponding minimum energy crossing points (MECPs) obtained by the mathematical algorithm proposed by Harvey et al. have also been used. Additionally, possible spin inversion processes are discussed using spin–orbit coupling (SOC) calculations. [ABSTRACT FROM AUTHOR]

Abstract: The gas-phase reaction of activation of C–C double bond of C2H4 by has been investigated using density functional theory (DFT) at the UB3LYP/6-311G(2d,p) level. The calculation results show that the reaction experiences rearranged process. On the basis of Hammond postulate, this is a typical ‘two-state reactivity’ (TSR) reaction. The involving crossing between the singlet and triplet potential energy surfaces has been discussed by means of the intrinsic reaction coordinate (IRC) approach used by Yoshizawa et al., and a minimum energy crossing point (MECP) that we obtained by the mathematical algorithm proposed by Harvey et al. has been also employed. [Copyright &y& Elsevier]