Title:

Interaction of molecular Rydberg states with metal surfaces

The interaction between highn Rydberg states of molecular hydrogen and metal surfaces has been investigated for the first time. Rydberg states of hydrogen possessing either 0 or 2 units of rotational angular momentum, defined by the quantum number N^{+} , and principal quantum numbers in the range n= 17 22 (for the N^{+}= 2 states) and n=4145 (for the N^{+}= 0 states) are directed at a grazing angle onto a metal surface (gold or aluminium). At a sufficiently close distance ionisation may occur via tunnelling of the Rydberg electron into the vacant metal conduction band. Any ions formed in the vicinity of the metal are extracted by the application of an electric field and information about the distance at which the ions are formed can be inferred from the magnitude of the applied field required for detection. Two novel effects are observed. Firstly, it appears that the rotation of the H2^{+} core has a significant effect on the ionisation properties of the Rydberg states in a manner akin to rotational autoionisation, such that the rotational energy of the core is given up to the Rydberg electron. Secondly, the surface ionisation profiles do not vary smoothly with applied field suggesting that at certain fields the feasibility of ionisation is either enhanced or reduced. A preliminary discussion of the origin of the structure is presented in terms of the crossings in the Stark map between the N^{+}= 0 and N^{+}= 2 Stark manifolds. The development of a theoretical model, and an associated Fortran program, involving the technique of complex scaling is also reported. The hydrogen molecules are modeled using an atomic hydrogen system which provides a good first approximation to the behaviour of the Rydberg electron for states with n > 5. Energies and linewidths, for states with principal quantum number n= 6 9 interacting with a model surface, are explicitly calculated at a range of surface separations. From this information, predictions of the ionisation behaviour expected for states of higher principal quantum number are presented.
