Quantum-chemical calculations on the mechanisms of reactions of W and W+ with N2O

The mechanisms of the reaction of W and W+ with the N2O were investigated at the CCSD(T)/[SDD+6-311G(d)]//B3LYP/[SDD+6-31G(d)] level of theory. It was shown that the reaction of W(7S) + N2O(1Σ+) is a multi-state process, involves several lower-lying electronic states of numerous intermediates and transition states, and leads to oxidation, WO(3Σ) + N2(1Σg+) with a negligible barrier and/or nitration, WN(4Σ) + NO(2P) with a barrier of 6.7 kcal/mol relative to reactants. The reaction of W+ with N2O, resemble its neutral analog, proceeds via the insertion and direct abstraction pathway, leads to oxidation and nitration of the W-center.