We combine multichannel electronic structure theory with quantum optimal control to derive femtosecond-time-scale Raman pulse sequences that coherently populate a valence excited state. For a neon atom, Raman target populations of up to 13% are obtained. Superpositions of the ground and valence Raman states with a controllable relative phase are found to be reachable with up to 4.5% population and arbitrary phase control facilitated by the pump pulse carrier-envelope phase. Analysis of the optimized pulse structure reveals a sequential mechanism in which the valence excitation is reached via a fast (femtosecond) population transfer through an intermediate resonance state in the continuum rather than avoiding intermediate-state population with simultaneous or counterintuitive (stimulated Raman adiabatic passage) pulse sequences. Our results open a route to coupling valence excitations and core-hole excitations in molecules and aggregates that locally address specific atoms and represent an initial step towards realization of multidimensional spectroscopy in the xuv and x-ray regimes.

• Received 9 October 2014

DOI:https://doi.org/10.1103/PhysRevA.92.013407