Decomposition rotational excitation

The rotational temperature of NO (A) in the HeJ/NO reaction was 1170 100 K, which was essentially independent of V. The similar rotational excitation for v = 0-5 levels was explained by the fact that the CT reaction occurs near resonantly because the RE of HeJ has a large latitude of 2 eV. Only 0.10 0.01 eV of the RE, which amounts to only 0.5% of the RE, is converted into the rotational energy of NO" (A). The rotational temperatures of NO (A) were slightly higher than those of Nf(B v = 0) and CO" (B v = 0). A higher rotational excitation is consistent with the fact that the HeJ/NO reaction proceeds through an intimate collision, where more conversion of the RE of HeJ into the rotational energy of the product NO" (A) ion becomes possible via decomposition of a non-linear complex. 

Sq is forbidden if the product R is in the state. Available data support this conclusion quite well. Symmetry arguments also indicate that the quenching of Pi to proceeds by the rotational excitation of RH. This is consistent with the observed increase in the metastable atom formation by D substitution. The mean life of the complex is assumed to be governed by two factors (a) the polarizability of RH, which determines the rate of decomposition of the complex back to reactants, and (b) the CH bond strength, which determines the rate of the decomposition of the complex to HgH and R. This model explains quite well the various differences observed among structurally similar paraffins in the quenching of atoms. 

Dynamical Effects of H h Rotational Excitation in Unimolecular Decomposition Activated by Hot Atom Substitution... 

Dynamic Effects of Rotational Excitation on Unimolecular Decomposition... 

These results tend to validate our earlier conclusions (20,21) about the importance of dynamical effects in the unimolecular decomposition of highly excited molecules. In that sense we feel that they must stand as a qualification of unimolecular rate models for such species. Interestingly, this work shows that this qualification is lessened under the more realistic condition of high rotational excitation. 

In yet another study in the pressure range 5-40 torr, but using a capacitively coupled rf discharge, the decomposition of NH3 followed an apparent zero order kinetics which was interpreted on the basis of a kinetic mechanism involving vibro-rotationally excited molecules. Figure 12 shows the degree of conversion of NHj as a function of the mean residence time within a tubular reactor. Simultaneous spectroscopic measurements at different positions along the reactor axis showed... 

The energy disposal and effective upper state lifetimes have been reproduced using classical trajectory calculations a quasi-diatomic assumption was made to determine the slope of the section through the upper potential energy surface along the N—a bond from the shape of the u.v. absorption profile. The only adjustable parameter was the assumption of a parallel transition in the quasi-diatomic molecule. In contrast, a statistical adiabatic channel model which assumed dissociation via unimolecular decomposition out of vibrationally and rotationally excited level in the ground electronic state (following internal con-... 

Figure 14. Spectra of the products of IRMPD of CH2CFC1 taken under conditions of higher decomposition yield than in Figure 13, brought about by addition of 1.6Torr Ar to 40mTorr of the precursor. At the time of observation, 45

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