Precision Spectroscopy in Cold Molecules: The Lowest Rotational Interval of He_{2}^{+} and Metastable He_{2}

Multistage Zeeman deceleration was used to generate a slow, dense beam of translationally cold He_{2} molecules in the metastable a ^{3}Σ_{u}^{+} state. Precision measurements of the Rydberg spectrum of these molecules at high values of the principal quantum number n have been carried out. The spin-rotational state selectivity of the Zeeman-deceleration process was exploited to reduce the spectral congestion, minimize residual Doppler shifts, resolve the Rydberg series around n=200 and assign their fine structure. The ionization energy of metastable He_{2} and the lowest rotational interval of the X^{+} ^{2}Σ_{u}^{+} (ν^{+}=0) ground state of ^{4}He_{2}^{+} have been determined with unprecedented precision and accuracy by Rydberg-series extrapolation. Comparison with ab initio predictions of the rotational energy level structure of ^{4}He_{2}^{+} [W.-C. Tung, M. Pavanello, and L. Adamowicz, J. Chem. Phys. 136, 104309 (2012)] enabled us to quantify the magnitude of relativistic and quantum-electrodynamics contributions to the fundamental rotational interval of He_{2}^{+}.