RESUMEN
Molecular helium represents a benchmark system for testing ab initio calculations on few-electron molecules. We report on the determination of the adiabatic ionization energy of the a ^{3}Σ_{u}^{+} state of He_{2}, corresponding to the energy interval between the a ^{3}Σ_{u}^{+} (v^{''}=0, N^{''}=1) state of He_{2} and the X^{+} ^{2}Σ_{u}^{+} (v^{+}=0, N^{+}=1) state of He_{2}^{+}, and of the lowest rotational interval of He_{2}^{+}. These measurements rely on the excitation of metastable He_{2} molecules to high Rydberg states using frequency-comb-calibrated continuous-wave UV radiation in a counterpropagating laser-beam setup. The observed Rydberg states were extrapolated to their series limit using multichannel quantum-defect theory. The ionization energy of He_{2} (a ^{3}Σ_{u}^{+}) and the lowest rotational interval of He_{2}^{+} (X^{+} ^{2}Σ_{u}^{+}) are 34 301.207 002(23)±0.000 037_{syst} cm^{-1} and 70.937 589(23)±0.000 060_{syst} cm^{-1}, respectively.
RESUMEN
The term values of the rotational levels of the first excited vibrational state of the electronic ground state of He 2 + with a rotational quantum number N + ≤ 13 have been determined with an accuracy of 1.2 × 10-3 cm-1 (â¼35 MHz) by multichannel-quantum-defect-theory-assisted Rydberg spectroscopy of metastable He2. Comparison of the experimental term values with the most accurate ab initio results for He 2 + available in the literature [W.-C. Tung, M. Pavanello, and L. Adamowicz, J. Chem. Phys. 136, 104309 (2012)] reveals inconsistencies between the theoretical and experimental results that increase with increasing rotational quantum numbers. The fundamental vibrational wavenumber of He 2 + was determined to be 1628.3832(12) cm-1 by fitting effective molecular constants to the obtained term values.
RESUMEN
Measuring spin-rotation intervals in molecular cations is challenging, particularly so when the ions do not have electric-dipole-allowed rovibrational transitions. We present a method, based on an angular-momentum basis transformation, to determine the spin-rotational fine structure of molecular ions from the fine structure of high Rydberg states. The method is illustrated by the determination of the so far unknown spin-rotation fine structure of the fundamentally important He_{2}^{+} ion in the X ^{2}Σ_{u}^{+} state. The fine-structure splittings of the v^{+}=0, N^{+}=1, 3, and 5 levels of He_{2}^{+} are 7.96(14), 17.91(32), and 28.0(6) MHz, respectively. The experiment relies on the use of single-mode cw radiation to record spectra of high Rydberg states of He_{2} from the a ^{3}Σ_{u}^{+} metastable state.
RESUMEN
The term values of all rotational levels of the 4He2+ X+ 2Σu+ (ν+=0) ground vibronic state with rotational quantum number N+ ≤ 19 have been determined with an accuracy of 8 × 10-4 cm-1 (â¼25 MHz) by multichannel-quantum-defect-theory-assisted Rydberg spectroscopy of metastable He2∗. Comparison of these term values with term values recently calculated ab initio by Tung et al. [J. Chem. Phys. 136, 104309 (2012)] reveals discrepancies that rapidly increase with increasing rotational quantum number and reach values of 0.07 cm-1 (â¼2.1 GHz) at N+ = 19.
RESUMEN
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}^{+}.