Contribution of forbidden orbits in the photoabsorption spectra of atoms and molecules in a magnetic field

In a previous work [Phys. Rev. A \textbf{66}, 0134XX (2002)] we noted a partial disagreement between quantum R-matrix and semiclassical calculations of photoabsorption spectra of molecules in a magnetic field. We show this disagreement is due to a non-vanishing contribution of processes which are forbidden according to the usual semiclassical formalism. Formulas to include these processes are obtained by using a refined stationary phase approximation. The resulting higher order in $\hbar$ contributions also account for previously unexplained ``recurrences without closed-orbits''. Quantum and semiclassical photoabsorption spectra for Rydberg atoms and molecules in a magnetic field are calculated and compared to assess the validity of the first-order forbidden orbit contributions.Comment: 12 pages, 6 figure

Observation of diffractive orbits in the spectrum of excited NO in a magnetic field

We investigate the experimental spectra of excited NO molecules in the diamagnetic regime and develop a quantitative semiclassical framework to account for the results. We show the dynamics can be interpreted in terms of classical orbits provided that in addition to the geometric orbits, diffractive effects are appropriately taken into account. We also show how individual orbits can be extracted from the experimental signal and use this procedure to reveal the first experimental manifestation of inelastic diffractive orbits.Comment: 4 fig

Semiclassical quantization of the hydrogen atom in crossed electric and magnetic fields

The S-matrix theory formulation of closed-orbit theory recently proposed by Granger and Greene is extended to atoms in crossed electric and magnetic fields. We then present a semiclassical quantization of the hydrogen atom in crossed fields, which succeeds in resolving individual lines in the spectrum, but is restricted to the strongest lines of each n-manifold. By means of a detailed semiclassical analysis of the quantum spectrum, we demonstrate that it is the abundance of bifurcations of closed orbits that precludes the resolution of finer details. They necessitate the inclusion of uniform semiclassical approximations into the quantization process. Uniform approximations for the generic types of closed-orbit bifurcation are derived, and a general method for including them in a high-resolution semiclassical quantization is devised