ABSTRACT: Reactions of PtX+ (X = F, Cl, Br, I) with methane have been investigated at the density functional theory (DFT) level. These reactions take place more easily along the low-spin potential energy surface. For HX (X = F, Cl, Br, I) elimination, the formal oxidation state of the metal ion appears to be conserved, and the importance of this reaction channel decreases in going as the sequence: X = F, Cl, Br, I. A reversed trend is observed in the loss of H2 for X = F, Cl, Br, while it is not favorable for PtI+ in the loss of either HI or H2. For HX eliminations, the transfer form of H is from proton to atom, last to hydride, and the mechanisms are from PCET to HAT, last to HT for the sequence of X = F, Cl, Br, I. One reason is mainly due to the electro
