Universal and nonuniversal statistical properties of levels and intensities for chaotic Rydberg molecules.

Abstract

We study Rydberg molecules taking into account the interaction between the rotational motion of the nuclei and the radial motion of the electron. This situation can be treated to a good approximation in quantum mechanics by the multichannel quantum-defect method which in turn has a well-defined classical limit. We are able to calculate very long sequences of levels and the corresponding amplitudes of wave packets. This allows us to study the statistical properties of both in detail. Our interest focuses on aspects of quantum chaos'' that can be particularly well understood in this case. Our main result is that, in a completely chaotic classical situation, where statistics of quantum-level spacings follow the expected universal Gaussian-orthogonal-ensemble behavior, and statistics of line intensities display the expected universal Porter-Thomas behavior, nonuniversal properties are explicitly contained in correlations between intensities and spacings, determined by the time needed for the classical system to mix on a length scale given by the quantum wavelength.