  We combine multi-channel electronic structure theory with quantum optimal
control to derive 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 phase control facilitated by the pump pulse carrier envelope
phase. Our results open a route to creating core-hole excitations in molecules
and aggregates that locally address specific atoms and represent the first step
towards realization of multidimensional spectroscopy in the xuv and x-ray
regimes.
