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<p>Rydberg electronic states of atoms and molecules are a special kind of excited species. As a classical particle, a Rydberg electron would move in a nearly zero-energy orbit with a negative eccentricity, and the motion can be even slower than its parent ionic core. It is thus possible to develop a general adiabatic approximation to decouple the Rydberg electronic degrees of freedom from those of the ionic core. In this review, we present a systematic formulation of such a theory based on the inverse Born–Oppenheimer (IBO) approximation, in contrast to the usual Born–Oppenheimer (BO) separation. It is shown that the IBO basis set is more suitable for Rydberg states than the BO approximation. Several important radiative and nonradiative processes involving Rydberg states are discussed.</p>

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The Inverse Born–Oppenheimer Approximation for Rydberg States in Atomic, Molecular and Optical Physics

  • 期刊论文

  • 发表日期：

    2026年6月2日

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  • Yi-Siang Wang,
  • Sheng D. Chao

摘要

Rydberg electronic states of atoms and molecules are a special kind of excited species. As a classical particle, a Rydberg electron would move in a nearly zero-energy orbit with a negative eccentricity, and the motion can be even slower than its parent ionic core. It is thus possible to develop a general adiabatic approximation to decouple the Rydberg electronic degrees of freedom from those of the ionic core. In this review, we present a systematic formulation of such a theory based on the inverse Born–Oppenheimer (IBO) approximation, in contrast to the usual Born–Oppenheimer (BO) separation. It is shown that the IBO basis set is more suitable for Rydberg states than the BO approximation. Several important radiative and nonradiative processes involving Rydberg states are discussed.