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The Stark effect in molecular Rydberg states is qualitatively different from the Stark effect in atomic Rydberg states because of the anisotropy of the ion core and the existence of rotational and vibrational degrees of freedom. These uniquely molecular features cause the electric-field-induced decoupling of the Rydberg electron from the body frame to proceed in several stages in a molecule. Because the transition dipole moment among the same-n* Rydberg states is much larger than the permanent dipole moment of the ion core, the decoupling of the Rydberg electron from the ion core proceeds gradually. In the first stage, analyzed in detail in this paper, l and N are mixed by the external electric field, while N+ is conserved. In the further stages, as the external electric field increases, N+, n*, and v+ are expected to undergo mixing. We have characterized these stages in n* = 13, v+ = 1 states of CaF. The large permanent dipole moment of CaF+ makes CaF qualitatively different from the other molecules in which the Stark effect in Rydberg states has been described (H[subscript 2], Na[subscript 2], Li[subscript 2], NO, and H[subscript 3]) and makes it an ideal testbed for documenting the competition between the external and CaF+ dipole electric fields. We use the weak-field Stark effect to gain access to the lowest-N rotational levels of f, g, and h states and to assign their actual or nominal N+ quantum number. Lowest-N rotational levels provide information needed to disentangle the short-range and long-range interactions between the Rydberg electron and the ion core. We diagonalize an effective Hamiltonian matrix to determine the l-characters of the 3 ≤ l ≤ 5 core-nonpenetrating 2Σ+ states and to characterize their mixing with the core-penetrating states. We conclude that the mixing of the l = 4, N−N+ = −4(g(−4)) state with lower-l [superscript 2]Σ+ states is stronger than documented in our previous multichannel quantum defect theory and long-range fits to zero-field spectra.National Science Foundation (U.S.) (grant CHE-0450876)National Science Foundation (U.S.) (grant CHE- 0749821

The Stark effect in Rydberg states of a highly polar diatomic molecule: CaF