Time and frequency resolved spectra of high molecular Rydberg states by dynamical computations

Abstract

The absorption spectrum of bound Rydberg states which can be detected by a delayed, pulsed field ionization is computed. The spectrum, measured for various delay times, provides information on the short and the longer time dynamics of high molecular Rydberg states. A quantitative dynamical theory, based on an effective Hamiltonian formalism is applied, illustrating the role of the Rydberg electron–core coupling and of an external electrical field in the delay-time dependent spectra. The sharpening of the spectra for longer delay times is reproduced by the dynamical computations. It is found that the overall intensity, as a function of the delay time before detection, is well described by a double exponential decay where the short lifetime is primarily a manifestation of the direct autoionization to the continuum, while the long lifetime is due to interseries coupling. Both lifetimes increase with the principal quantum number of the Rydberg states. The notion of trapped “reservoir states” is illustrated by the computational results, with special reference to a kinetic model analysis. The role of the initially optically accessed state(s) and of the depth of detection, in particular with regard to the intensity, is demonstrated. The effect of varying the strength of an external dc field in the time interval prior to the detection is illustrated by the dynamical computations, with respect to both the decay kinetics and the intensity of the spectrum.