Multireference perturbation theory (MRPT2) study on N2O capture and activation by excited states of Rh atom and cation

Nitrous oxide (N2O) is an intermediate compound in three-ways exhaust-pipes catalysis. Rh and Rh+ + N2O reactions are calculated at ab initio MRPT2 level, in Cs symmetry and for many multiplicities to find N2O capture and activation. Rh ground state does not capture N2O; however some excited states spontaneously capture and activate it, where only RhN2O (b 6A′) and (e 8A″) activate N2O: RhN2O → RhO + N2 and RhN2O → RhN2 + O, respectively but never break N–N bond. Rh+ ground state weakly capture N2O, but only one Rh+ excited state captures and activates N2O. N2O activation by Rh atom and cation do not involve any transition states.