Rydberg Wavepackets Kepler and Precessional Periods

The energy spacing between consecutive (n — 1/2, n + 1/2) members of a Rydberg series is 2hdft/n 3, where 3 is the Rydberg constant (109737 cm-1) and n is the (non-integer) effective principal quantum number. The intensities of transitions between valence and Rydberg states are controlled by a 

The center of the Rydberg wavepacket, (r)t, undergoes periodic radial oscillations, analogous to the planetary motions (Kepler orbits). The Kepler period of (r)t for the Rydberg wavepacket with center-n, n enter, is 

Once again, the quadrupole splittings are integer multiples of a common factor, and if several Z/j -components are excited at t — to, the Rydberg wavepacket will precess about N+ and exhibit grand rephasings. 

All of the vector precession pictures associated with the various Hund s coupling cases correspond to experimentally realizable wavepacket motions, provided that molecules with energy level patterns well described by one of the Hund s cases (see Section 3.2.1) can be suitably plucked. (Texier and Jungen, 1998 and 1999 Smith, et al, 2003a). 

Between the direct and doorway-mediated limiting cases one finds sequential 

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