Symmetry of molecular Rydberg states revealed by XUV transient absorption spectroscopy

Transient absorption spectroscopy is utilized extensively for measurements of bound- and quasibound-state dynamics of atoms and molecules. The extension of this technique into the extreme ultraviolet (XUV) region with attosecond pulses has the potential to attain unprecedented time resolution. Here we apply this technique to aligned-in-space molecules. The XUV pulses are much shorter than the time during which the molecules remain aligned, typically [Formula: see text] 100 fs. However, transient absorption is not an instantaneous probe, because long-lived coherences re-emit for picoseconds to nanoseconds. Due to dephasing of the rotational wavepacket, it is not clear if these coherences will be evident in the absorption spectrum, and whether the properties of the initial excitations will be preserved. We studied Rydberg states of N[Formula: see text] and O[Formula: see text] from 12 to 23 eV. We were able to determine the polarization direction of the electronic transitions, and hence identify the symmetry of the final states.