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5.7. DESCRIPTION OF THE REACTION KINETICS (DB) has been employed. The validity of using DB with respect to CO2 plasmas has been discussed in Kozák et al. [64]. 5.7.3 Vibrational kinetics The set of reactions involving symmetric modes has been discussed in chapter 4. The confidence in the rate coefficients of reactions involving these low lying vibrational levels of symmetric modes have been established by experiments on CO2 lasers [185]. Generally, the rate co-efficients of reactions involving higher levels are determined by spectroscopic methods [238]. However detailed studies are not available for reactions involving molecules excited along asymmetric mode. In order to over come the lack of experimental data, theoretical methods have to be employed to calculate rate coef- ficients. Among the theoretical methods available Schwartz-Slawsky-Herzfeld (SSH) theory is quite successful [219] for many diatomic molecules and is easy to implement with formulas in closed form [64, 218]. SSH theory is most widely used to calculate a transition probability for change in quantum numbers of interacting molecules, P m,m+1 [239] (probability for example re- n,n−1 action R4) which when multiplied with gas collision rate (k0) gives rate coefficient of the reaction [36] (effectively integrating the probability over velocity distribution) km,m+1 = k P m,m+1 (5.7) n,n−1 0 n,n−1 From this equation it becomes clear that the rate-coefficients cannot exceed gas-collision rates unless the cross-section used for integrating the probability over velocity distri- bution is much higher than the collisional cross-section of background molecules as in ion-electron interactions. However, SSH theory is developed for very short range re- pulsive forces and fails for long range forces (polar molecules or multi-pole interaction) [239], hence gas-collision rates should serve as an upper limit for rate coefficients cal- culated from this theory. There are other theories which are more suitable to calculate the rate-coefficients or probabilities of transitions where long range forces are important like Sharma and Brau [240] and Forced Harmonic Oscillator (FHO) theory [241]. FHO theory is also more suitable to be applied for higher vibrational levels, where SSH ap- plicability is doubtful [241]. Nonetheless, none of these theories have been yet tested, experimentally, for CO2 asymmetric mode vibrational kinetics. As has been mentioned before, there is a dearth of experimental reports on the rate coefficients of VV transfer in asymmetric mode. However, an estimate on the rate- coefficient can be drawn from one of the few papers available [242]. To measure the rate 128PDF Image | Understanding CO2 containing non-equilibrium plasmas
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