Theoretical investigation of vibrational relaxation of NO(2 Π), O), and N) in collisions with O(3P)

Abstract

The vibrational relaxation of NO(2Π), O, and in collisions with O(3P) is investigated by means of classical trajectories (NO, O2) and quantum mechanical (N2) scattering calculations N2 using calculated potential energy surfaces. For NO and O2, intermediate collision complexes are formed and the relaxation rate coefficients are large, of the order of 5×10-11 cm3 s−1 and 2×10-12 cm3 s−1, respectively, at room temperature. The agreement with available experimental data for NO is very good. The calculated rate coefficient for O2, however, is about two times smaller than the measured rate coefficient. In both cases, the relaxation rate coefficient is slightly smaller than the complex formation or twice the atom exchange rate. Oxygen atoms colliding with N2, on the other hand, do not form a collision complex; the potential energy surfaces for NP) are purely repulsive. The calculated room temperature rate coefficient is on the order of 1×10-15 cm3 s−1; it underestimates the measured rate coefficient by about a factor of 4.