We present a general theoretical treatment and calculations of the fine and hyperfine structures in the spectra of high-$n$ molecular Rydberg states in static uniform electric fields. The treatment combines (i) multichannel quantum-defect theory and long-range polarization models to determine the field-free energies of $n\ell$ Rydberg states of the molecules ($\ell$ is the orbital-angular-momentum quantum number of the Rydberg electron), (ii) a matrix-diagonalization approach to calculate the Stark shifts including the hyperfine structure, and (iii) sequences of angular-momentum basis transformations to predict the line positions and intensities in Stark spectra as they would be observed in single or multiphoton excitation sequences. To clarify how the molecular rotation and the nuclear spins influence the fine and hyperfine structure of molecular Rydberg-Stark spectra, we compare calculated spectra of ortho-${\mathrm{D}}_2$ with a ${\mathrm{D}}_2^{+}$ ion core in the rotational ground state ($N^{+}=0$) for total nuclear spins $I$ of 0 (i.e., without hyperfine structure) and 2 (i.e., with hyperfine structure) with the corresponding spectra of para-${\mathrm{H}}_2$ with an ${\mathrm{H}}_2^{+}$ ion core in the first excited rotational state ($N^{+}=2$) but zero nuclear spin ($I=0$). The calculations show that the hyperfine interaction alone does not significantly modify the Stark effect, but splits each Stark state by almost exactly the hyperfine Fermi-contact splitting of the ion core. In contrast, the molecular rotation, which is coupled both to the ion-core electron spin by the magnetic spin-rotation interaction and to the Rydberg-electron orbital motion by the core-polarization and charge-quadrupole interactions, induces Stark-state-specific splittings that significantly differ from the spin-rotation splitting of the ($N^{+}=2$) ion core.

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• Atomic & molecular structure
• Electronic excitation & ionization
• Fine & hyperfine structure
• Stark effect
• Atomic & molecular beams
• Molecules
• Rydberg atoms & molecules
• Photoexcitation
• Photoionization