Journal of Physical Chemistry A, Vol.102, No.47, 9570-9576, 1998
A uniform theory of preparation, dissociation, and product formation in the decay of overlapping resonances
We present a uniform treatment of (the weak field) preparation and evolution of a superposition of overlapping resonances. We show that the manner of (the optical) preparation has profound effect on the observed decay dynamics when resonances overlap. Depending on the preparation pulse width, we find that the time evolution of the population and the fluorescence are different and that, contrary to common wisdom, fluorescence is not proportional to the autocorrelation ("survival") function. Moreover, we find that the interference between decaying overlapping resonances gives rise to transient surges in the total bound-state population. We also derive an analytic expression for the evolution of the various products states from inception to assumption of their long-time limits. We find that initially the formation of the products is dominated by off-resonance processes in which products appear and disappear instantaneously with the pulse. Only after the pulse vanishes does the build up of the product populations take place over time scales related to spectral features. This average buildup is shown to be modulated by bursts due to interference between resonances.
Keywords:BOUNDARY-CONDITIONS;REACTION-RATES;LASER-PULSES;ONE-PHOTON;DYNAMICS;PHOTODISSOCIATION;PREDISSOCIATION;APPROXIMATION;SCATTERING;IBR