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5.5. SUMMARY OF PART I energy in the asymmetric stretch mode ν3, since the higher quantum on this mode implies a larger separation between CO and O species and eventually dissociation. This separa- tion is achieved at dissociation energy via inter-system crossing (from ground electronic state to 1B2 electronic state) at 5.1 eV [36, 203]; a schematic of potential energy with average separation between CO and O shown in figure 5.3 illustrates this inter-system crossing. It has to be noted the energy of 20th vibrational level of asymmetric mode possesses 5.1 eV. Also, a major fraction of electron energy is transferred to excite the lower quanta of asymmetric mode (when Te = 1-3 eV) which is further enhanced by CO formation [35] ; as can be seen from equation 5.4, VT relaxation is much slower in this mode hence higher quanta in this mode can be populated. Also from 5.4, VV’ transfer of energy from asymmetric mode to the symmetric modes is very slow. Consequently very high densities of vibrationally excited molecules can be achieved in asymmetric mode easily compared with symmetric modes [36]. Although, the vibrational distribution is considered for individual states, dissociation in a poly-atomic molecule occurs from a vibrational quasi-continuum [36, 227]. For CO2 the nature of quasi-continuum depends on the relative number of quanta of asymmetric and symmetric excited; the nature of vibrations in quasi-continuum can be purely asym- metric mode or in some cases made up of all the modes. The vibrations are not mixed when Tva ≪ Tvs and when the quanta of vibration on asymmetric mode exceeds the av- erage number of quanta on symmetric mode significantly. Conversely, when Tva ≈ Tvs, then the nature of continuum is mixed and also one temperature model can be used. However, for CO2 dissociation under non equilibrium the first case is more common and hence, more useful for the current study [36]. 5.5 Summary of part I The part-I of this chapter introduces the basic notions of vibrational distributions and the method to calculate dissociation rates from them in CO2 plasmas. The main ideas from this part on which the next part is built are • Vibrational excitation is very important in achieving very high energy efficiencies in dissociation of molecules. • Kinetic modeling can be used to calculate the vibrational distributions which can then further used to infer the dissociation rates from the population of highly ex- cited vibrational states. 119PDF Image | Understanding CO2 containing non-equilibrium plasmas
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