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Unified theory of bound and scattering molecular Rydberg states as quantum maps

Barbara Dietz, Maurice Lombardi, Thomas H Seligman

physics.chem-pharXiv:physics/0402077

Abstract

Using a representation of multichannel quantum defect theory in terms of a quantum Poincaré map for bound Rydberg molecules, we apply Jung's scattering map to derive a generalized quantum map, that includes the continuum. We show, that this representation not only simplifies the understanding of the method, but moreover produces considerable numerical advantages. Finally we show under what circumstances the usual semi-classical approximations yield satisfactory results. In particular we see that singularities that cause problems in semi-classics are irrelevant to the quantum map.

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