Zero-Quantum-Defect Method and the Fundamental Vibrational Interval of H_{2}

The fundamental vibrational interval of H_{2}^{+} has been determined to be ΔG_{1/2}=2191.126 614(17) cm^{-1} by continuous-wave laser spectroscopy of Stark manifolds of Rydberg states of H_{2} with the H_{2}^{+} ion core in the ground and first vibrationally excited states. Extrapolation of the Stark shifts to zero field yields the zero-quantum-defect positions -R_{H_{2}}/n^{2}, from which ionization energies can be determined. Our new result represents a 4-order-of-magnitude improvement compared to earlier measurements. It agrees, within the experimental uncertainty, with the value of 2191.126 626 344(17)(100) cm^{-1} determined in nonrelativistic quantum electrodynamic calculations [V. Korobov, L. Hilico and J.-Ph. Karr, Phys. Rev. Lett. 118, 233001 (2017)PRLTAO0031-900710.1103/PhysRevLett.118.233001].

Determination of the Interval between the Ground States of Para- and Ortho-H_{2}.

Nuclear-spin-symmetry conservation makes the observation of transitions between quantum states of ortho- and para-H_{2} extremely challenging. Consequently, the energy-level structure of H_{2} derived from experiment consists of two disjoint sets of level energies, one for para-H_{2} and the other for ortho-H_{2}. We use a new measurement of the ionization energy of para-H_{2} [E_{I}(H_{2})/(hc)=124 417.491 098(31) cm^{-1}] to determine the energy separation [118.486 770(50) cm^{-1}] between the ground states of para- and ortho-H_{2} and thus link the energy-level structure of the two nuclear-spin isomers of this fundamental molecule. Comparison with recent theoretical results [M. Puchalski et al., Phys. Rev. Lett. 122, 103003 (2019)PRLTAO0031-900710.1103/PhysRevLett.122.103003] enables the derivation of an upper bound of 1.5 MHz for a hypothetical global shift of the energy-level structure of ortho-H_{2} with respect to that of para-H_{2}.

Dissociation Energy of the Hydrogen Molecule at 10

The ionization energy of ortho-H_{2} has been determined to be E_{I}^{o}(H_{2})/(hc)=124 357.238 062(25) cm^{-1} from measurements of the GK(1,1)-X(0,1) interval by Doppler-free, two-photon spectroscopy using a narrow band 179-nm laser source and the ionization energy of the GK(1,1) state by continuous-wave, near-infrared laser spectroscopy. E_{I}^{o}(H_{2}) was used to derive the dissociation energy of H_{2}, D_{0}^{N=1}(H_{2}), at 35 999.582 894(25) cm^{-1} with a precision that is more than one order of magnitude better than all previous results. The new result challenges calculations of this quantity and represents a benchmark value for future relativistic and QED calculations of molecular energies.