Rydberg states time evolution

The fragment excited-state NO(A2S+) is a molecular 3r Rydberg state, and we shall refer to this as NO(A, 3s). The observed NO(A, 3.v) product state distributions supported the notion of a planar dissociation involving restricted intramolecular vibrational energy redistribution (IVR) [176]. A scheme for studying NO dimer photodissociation dynamics via TRPES is depicted in Fig. 25. The NO(A, 3.v) + NO(X) product elimination channel, its scalar and vector properties, and its evolution on the femtosecond time scale have been discussed in a number of recent publications (see Ref. [175] and references cited therein). 

The discovery that classical periodic motions of the electron can account for the oscillations in photoabsorption spectra is an elegant experimental connection between classical and quantal theories, as well as being a striking demonstration of the Gutzwiller formalism [2], Over the last few years, experimentally created wave-packets have been used to identify the corresponding periodic motions. In these empirical studies, a Rydberg wave-packet is formed from a low-lying state by a short laser pulse and the time evolution of this wave-packet is probed by a second laser pulse. 

Y. Komninos, C.A. Nicolaides, Effect of the Rydberg states on the time evolution of non-stationary states below or just above the ionization threshold, Phys. Rev. A 72 (2005) 032716. 

Because it can be efficient and selective, field ionization of Rydberg atoms has become a widely used tool.1 Often the field is applied as a pulse, with rise times of nanoseconds to microseconds,2"4 and to realize the potential of field ionization we need to understand what happens to the atoms as the pulsed field rises from zero to the ionizing field. In the previous chapter we discussed the ionization rates of Stark states in static fields. In this chapter we consider how atoms evolve from zero field states to the high field Stark states during the pulse. Since the evolution depends on the risetime of the pulse, it is impossible to describe all possible outcomes. Instead, we describe a few practically important limiting cases. 

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