Communication: Test of quantum chemistry in vibrationally hot hydrogen molecules.

Precision measurements are performed on highly excited vibrational quantum states of molecular hydrogen. The v = 12, J = 0 - 3 rovibrational levels of H2 (X1S+ g), lying only 2000 cm-1 below the first dissociation limit, were populated by photodissociation of H2S and their level energies were accurately determined by two-photon Doppler-free spectroscopy. A comparison between the experimental results on v = 12 level energies with the best ab initio calculations shows a good agreement, where the present experimental accuracy of 3.5 × 10-3 cm-1 is more precise than theory, hence providing a gateway to further test theoretical advances in this benchmark quantum system. [ABSTRACT FROM AUTHOR]