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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 3495-3505 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a simple model to evaluate the degree of l and ml mixing in high Rydberg states that results from perturbations caused by weak, homogeneous dc electric fields and static ions. This model predicts the lifetime of these states qualitatively and explains several seemingly contradictory observations obtained using zero-kinetic-energy (ZEKE) photoelectron spectroscopy. The presence of a small homogeneous dc electric field and a few ions in the sample volume causes ml mixing in general as well as l mixing, both of which contribute to the lengthening of the lifetimes. Consequently, the lifetime lengthening appears to be insensitive to the sample pressure. The effect of the dc electric field on the lifetime is complex. Although the electric field results in l mixing, with increasing field strength it inhibits ml mixing, and, at still higher field strength, induces ionization. The variation of the lifetimes with ion concentration is also complicated. At low ion concentration, the ml mixing varies across the Stark manifold of Rydberg states that belong to the same principal quantum number, so that different states have different lifetimes. At higher ion concentration, l and ml mixing are more uniform, which lengthens the lifetimes and makes them more similar across the Stark manifold. At still higher concentrations, collisional ionization dominates, which shortens the lifetimes.
    Type of Medium: Electronic Resource
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