Abstract
Recently a high precision spectroscopic investigation of the EF^1\Sigma_g^+ - X^1\Sigma_g^+ system of molecular hydrogen was reported yielding information on QED and relativistic effects in a sequence of rotational quantum states in the X^1\Sigma^+_g$ ground state of the H_2 molecule [E.J. Salumbides et al., Phys. Rev. Lett. 107, 043005 (2011)]. The present paper presents a more detailed description of the methods and results. Furthermore, the paper serves as a stepping stone towards a continuation of the previous study by extending the known level structure of the EF^1\Sigma^+_g state to highly excited rovibrational levels through Doppler-free two photon spectroscopy. Based on combination differences between vibrational levels in the ground state, and between three rotational branches (O, Q and S branches) assignments of excited EF^1\Sigma^+_g levels, involving high vibrational and rotational quantum numbers, can be unambiguously made. For the higher EF^1\Sigma^+_g levels, where no combination differences are available, calculations were performed using the multi-channel quantum defect method, for a broad class of vibrational and rotational levels up to J=19. These predictions were used for assigning high-J EF-levels and are found to be accurate within 5 cm^-1.
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