Rydberg state decay in inhomogeneous electric fields

Abstract

An extension of the model of Merkt and Zare [J. Chem. Phys. 101, 3495 (1994)] is presented to describe the effects of static inhomogeneous electric fields, which arise experimentally from combinations of applied (or stray) homogeneous fields and the presence of charged particles, on Rydberg states of atoms and molecules. The effect of an arbitrary number of charged particles is included and the effects of nonzero quantum defects are investigated. A quantization axis rotation procedure is defined, allowing clear distinction between homogeneous and inhomogeneous field effects. Calculations are reported of the time-dependent decay of a coherent population of eigenstates for n=20, 33, and 50, involving diagonalization of the full n2×n2 matrix. Calculations are also carried out for n=100 by pre-diagonalization of the full homogeneous field perturbation followed by a restricted basis set diagonalization for the inhomogeneous part of the perturbation. The inclusion of nonzero quantum defects has a substantial impact on the ml mixing, confining significant mixing to a narrow range of radial and angular positions of the ion. An applied homogeneous field of order the Inglis-Teller field is required in combination with the field due to the ions. The dynamics are very different according to whether np or nf series carry the transition probability. For np-state population, the maximum stabilization is achieved at ion-Rydberg distances of around 5n2a0, with the ion almost perpendicular to the applied homogeneous field. For an initial nf population the ion perturbation may have a destabilizing effect at sufficiently small homogeneous field (⩽0.1FIT). Significant effects of laser polarization on the stability are reported. Calculations for a realistic pseudo-random distribution of ions and Rydbergs suggest that ml mixing by ions will never reach the complete mixing limit, but that at least an order of magnitude stabilization is achievable under a restricted range of conditions.