Precision measurements and test of molecular theory in highly excited vibrational states of H2 (v = 11)

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Abstract

Accurate EF1Σg+-X1Σg+ transition energies in molecular hydrogen were determined for transitions originating from levels with highly excited vibrational quantum number, v = 11, in the ground electronic state. Doppler-free two-photon spectroscopy was applied on vibrationally excited H2∗, produced via the photodissociation of H2S, yielding transition frequencies with accuracies of 45 MHz or 0.0015 cm−1. An important improvement is the enhanced detection efficiency by resonant excitation to autoionizing 7 pπ electronic Rydberg states, resulting in narrow transitions due to reduced ac-Stark effects. Using known EF level energies, the level energies of X(v = 11, J = 1, 3–5) states are derived with accuracies of typically 0.002 cm−1. These experimental values are in excellent agreement with and are more accurate than the results obtained from the most advanced ab initio molecular theory calculations including relativistic and QED contributions.

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Trivikram, T. M., Niu, M. L., Wcisło, P., Ubachs, W., & Salumbides, E. J. (2016). Precision measurements and test of molecular theory in highly excited vibrational states of H2 (v = 11). Applied Physics B: Lasers and Optics, 122(12). https://doi.org/10.1007/s00340-016-6570-1

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