Ab initio molecular dynamics study of the reaction of U+ and U2+ with H2O in the gas phase: direct classical trajectory calculations.

The gas phase reactions of U(+) and U(2+) with H2O were investigated using an ab initio molecular dynamics method. All of the information along the minimum energy path were calculated with density functional theory (DFT) and coupled cluster methods. For U(+) with H2O, the molecular dynamics simulations yield a branching ratio of 86% for the H2 elimination channel to 14% for the H atomic elimination channel in agreement with the quadruple ion trap mass spectrometry (QIT/MS) experimental ratio of 91% to 9%. In the case of U(2+) + H2O, there is a crossing of the potential energy surfaces (PES) after the first transition state. Crossing seams between the PES and possible spin inversion processes were studied by means of the intrinsic reaction coordinate (IRC) approach. For U(2+) with H2O, all trajectories are corresponds to H atom elimination channel, this is consistent with the Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) experimental results. The chemical bonding evolution along the reaction pathways was discussed by using topological methodologies of the electron localization function (ELF).