Stationary wavefunctions and assignment

CH30N0(5i) for three selected resonance energies. The assignment in terms of vibrational quantum numbers to and n is described in the text. The dashed contours in the upper part represent the Si-state PES. The magnitudes of the wavefunctions in the exit channel are very much smaller than in the inner region of the potential. In order to make the tails of the wavefunctions perceptible the contours are chosen in a nonuniform way  

In order to make this discussion a little more quantitative we cast fttot(E) into a direct part, dir(E), which varies smoothly with energy, and an indirect part, ind E), which changes rapidly in the neighborhood of a resonance. dir and Find represent the nonresonant and the resonant parts of tof, respectively. The idea is to utilize the approximate expression for the time-dependent wavepacket to construct the indirect part by virtue of Equation (4.11). Using expansion (7.18) for the inner part of the wavepacket, damping each term according to (7.14), and taking the 

the stationary wavefunction becomes on resonance essentially a bound-state wavefunction with an amplitude which is proportional to the corresponding lifetime. The larger the survival time in the well region the larger is the magnitude of the stationary wavefunction. 

In the light of the above discussion the photodissociation of CH3ONO proceeds in the following way, 

The first step describes the excitation of a quasi-bound vibrational level in the excited electronic state with quantum numbers (m, n ). The second step represents the dissociation of the intermediate compound due to coupling to the continuum induced by energy redistribution inside the shallow well. 

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