Electronically Non-Adiabatic Channel of NO Synthesis

Probability of Formation of Intermediate N20 ( S+) Complex in Electronically Non-Adiabatic Channel of NO Synthesis 

The probability of formation of the intermediate complex N20 ( S+) in the non-adiabatic chaimel of NO synthesis can be found by summation of independent transitions from an initial triplet term (quantum number v) to any singlet S+ terms (Figs. 6-7, and 6-8 Osherov, 1965 Macheret et al., 1978)  

Here the lower summation limit A Dmin = ( o -ex)/5 = 6 - i o is the activation barrier of formation of the complex N20 ( i +) without changing vibrational quantum number V (see Fig. 6-7) and ex is the kinetic energy of the relative O-N2 motion. The Landau-Zener factors don t change a lot with Ad, whereas the Frank-Condon factors abruptly decrease at higher differences A d in vibrational quantum numbers during transition. Summation (6-21) gives the formation probability of N20 ( i +)  

Probability (6-22) depends on the vibrational and translational (ex) energy of reagents. It can be integrated over the Maxwellian distribution for kinetic energies of relative O-N2 motion to get the probability as a function of N2 vibrational quantum number and translational gas temperature  

At relatively high translational gas temperatures ( In 1), overcoming the activa-tionbarrier Eq for formation of an intermediate complex is mostly due to the translational temperature of reagents and is limited by the Maxwellian factor exp(- o/ To)  

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Formation of Intermediate N20 ( E+) Complex in Electronically Non-Adiabatic Channel of NO Synthesis. Estimate the maximum gas temperature To, when the formation of the intermediate N20 ( E+) complex proceeds as a multi-quantum transition and is determined by the vibrational energy of N2 molecules. Use relations (6-25) and (6-26) and estimate the probability of the multi-quantum transition. Explain why this mechanism is a preferred one in cold plasma-chemical systems. 

The electronically non-adiabatic channel aMb Nc of NO synthesis (Fig. 6-6) proceeds through the formation and decay of an intermediate long-lifetime vibrationally excited complex ... 

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