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VIOLATION OF MULLIKEN'S RULE FOR RYDBERG STATES

Please use this identifier to cite or link to this item: http://hdl.handle.net/1811/30608

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Title: VIOLATION OF MULLIKEN'S RULE FOR RYDBERG STATES
Creators: Altunata, Serhan N.; Coy, Stephen L.; Field, R. W.
Issue Date: 2005
Abstract: The results of \textit{ab-initio} $\mathbf{R}$-matrix calculations display profound deviations from Mulliken's rule in the continuum electronic structure of CaF. In the $1-D$ effective potential for the electronic motion, a shape resonance induces a crossover from short-range Mulliken-type dynamics to long-range dipole-mediated dynamics. This effect is visible in the scattering matrix as well as the photoionization cross-sections and photoelectron anisotropies. The non-Mulliken behavior can be exploited by $l$-selective detection of Rydberg dynamics and spectra, revealing the $l$-decomposition of molecular eigenstates.
URI: http://hdl.handle.net/1811/30608
Other Identifiers: 2005-TI-01
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