Classical trajectories complex mode

For better comparison of theoretical predictions for different-order processes, we have plotted the quantum Fano factors for both interacting modes in the no-energy-transfer regime with N = 2 — 5 and r = 5 in Fig. 7. One can see that all curves start from F w(0) = 1 for the input coherent fields and become quasistationary after some relaxations. The quantum and semiclassical Fano factors coincide for high-intensity fields and longer times, specifically for t > 50/(Og), where il will be defined later by Eq. (54). In Fig. 17, we observe that all fundamental modes remain super-Poissonian [F (t) >1], whereas the iVth harmonics become sub-Poissonian (F (t) < 1). The most suppressed noise is observed for the third harmonic with the Fano factor 0.81. In Fig. 7, we have included the predictions of the classical trajectory method (plotted by dotted lines) to show that they properly fit the exact quantum results (full curves) for the evolution times t > 50/(Og). The small residual differences result from the fact that the amplitude r was chosen to be relatively small (r = 5). This value does not precisely fulfill the condition r> 1. We have taken r = 5 as a compromise between the asymptotic value r oo and computational complexity to manipulate the matrices of dimensions 1000 x 1000. Unfortunately, we cannot increase amplitude r arbitrary due to computational limitations. 

From the results of classical trajectory calculations intrinsic non-RRKM behavior has been predicted for ethane dissociation, ethyl radical dissociation,and methyl isocyanide isomerization. These predictions are supported by classical trajectory calculations for model H-C-C -> H + C=C dissociation. To generalize, classical trajectory calculations have predicted intrinsic non-RRKM behavior for molecules with isolated high frequency modes [e.g, CH3NC, clusters like Li (H20)j, and van der Waals molecules], molecules like acetylene with linear geometries for which bending and stretching motions are nearly separable, and molecules with tight activated complexes. 

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