Periodic Orbit Theory for Rydberg Atoms in External Fields

Although hydrogen in external fields is a paradigm for the application of periodic orbits and the Gutzwiller trace formula to a real system, the trace formula has never been applied successfully to other Rydberg atoms. We show that spectral fluctuations of general Rydberg atoms are given with remarkable precision by the addition of diffractive terms. Previously unknown features in atomic spectra are exposed: there are new modulations that are neither periodic orbits nor combinations of periodic orbits; `core-shadowing’ generally decreases primitive periodic orbit amplitudes but can also lead to increases.