Theoretical study of the reactivity of X(3P) (X=Ge, Sn, Pb) with N2O(X1Σ)

The reactivity of X(3P) (X=Ge, Sn, Pb) with N2O(X1Σ) on both singlet and triplet potential energy surfaces have been investigated at the B3LYP level of theory. To accurately evaluate the activation barrier and reaction energy, the coupled cluster single point calculations using the B3LYP structures is performed. The calculated results are in good agreement with experimental observations. The X(P3)+N2O(X1Σ)→XO(X1Σ)+N2(X1Σg+) (X=Ge, Sn, and Pb) reactions that Arthur Fontijn has been observed are spin-forbidden for formation of ground state products in the experiments. The present paper is discussed with the aid of the direct abstraction (DA) mechanism (also called the surface crossing model), a correlation argument based on separated fragments X+O+N2 can explain the inefficiency of the X(P3)+N2O(X1Σ)→XO(X1Σ)+N2(X1Σg+) (X=Ge, Sn, and Pb) reactions at 298 K by the need to switch electron configurations along low-energy adiabatic paths from ground-state reactants to energetically accessible XO(X1Σ)+N2(X1Σg+) product states.