Vibrational relaxation of O2(X3Σ(-)g, v = 6-8) by collisions with O2(X3Σ(-)g, v = 0): solution of the problems in the integrated profiles method.

The linear kinetic analysis called the integrated profiles method (IPM) makes it simple to analyze the multistep relaxation processes of vibrational manifold. The problem that plots for linear regression in the IPM analysis cannot be made, however, has been found in the study of self relaxation of O2(X3Σ(-)g, v = 6-8). The cause of the problem is the identical time-dependence of the populations of the adjacent vibrational levels. An addition of CF4 into the system made a difference in the time profiles and enabled us to make IPM analysis and determine the rate coefficients. In the experiments, a gaseous mixture of O3/O2/CF4 in an Ar carrier at 298 K was irradiated at 266 nm, and the direct photoproduct O2(X3Σ(-)g, v = 6-9) from O3 was detected by laser-induced fluorescence (LIF)in the B3Σu-X3Σ(-)g transition. Time-resolved LIF intensities of O2(X3Σ(-)g, v) at various pressures of O2 and fixed pressure of CF4 were recorded. The resulting rate coefficients for v = 6−8 correlate smoothly with those for v ≤ 5 and v ≥ 8 reported previously.The vibrational-level dependence (v = 2-13) of the rate coefficients for relaxation of O2(X3Σ(-)g, v) by O2 is accounted for by the balance between the harmonic transition probabilities and the energy defect in the V-V energy-transfer mechanism.