Theoretical study of the activation of CH4 – nFn (n = 1–3) molecules by platinum in the gas-phase
Abstract The gas-phase reactions of fluorocarbon compounds CH 4 –  n F n ( n  = 1–3) with Pt ( 3 D, 1 S) 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 CH 3 F with Pt ( 3 D, 1 S) experiences a rearrangement process to generate counterintuitive production (CH 2 F−PtH). CH 2 F 2 and CHF 3 activation by Pt ( 3 D, 1 S) 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.