We present experimental observations of K_{β} emission from highly charged Mg ions at solid density, driven by intense x rays from a free electron laser. The presence of K_{β} emission indicates the n=3 atomic shell is relocalized for high charge states, providing an upper constraint on the depression of the ionization potential. We explore the process of state relocalization in dense plasmas from first principles using finite-temperature density functional theory alongside a wave-function localization metric, and find excellent agreement with experimental results.