First-principles electronic structure calculations of the excited states of Yb(2+)-doped SrCl(2) crystals up to 65,000 cm(-1) reveal the existence of unexpected excited states with double-well potential energy surfaces and dual electronic structure lying above and very close in energy to the 4f(13)5d manifold, with which they interact strongly through spin-orbit coupling. The double-well energy curves result from avoided crossings between Yb-trapped exciton states (more stable at short Yb-Cl distances) and 4f(13)6s impurity states (more stable at long Yb-Cl distances); the former are found to be preionization states in which the impurity holds the excited electron in close lying empty interstitials located outside the YbCl(8) moiety. Spin-orbit coupling between the double-well states and the lower lying 4f(13)5d impurity states spreads the dual electronic structure character to lower energies and, hence, the instability of the divalent oxidation state is also spread. To some extent, the dual electronic structure (impurity-trapped exciton-impurity state) of some excited states expresses and gives support to hypotheses of interaction between Yb(2+) and Yb(3+) pairs proposed to understand the complex spectroscopy of the material and conciliates these hypotheses with interpretations in terms of the existence of only one type of Yb(2+) defect. The results presented confirm the presence of impurity states of the 4f(13)6s configuration among the 4f(13)5d manifolds, as proposed in literature, but their energies are very different from those assumed. The Yb-trapped excitons found in this chloride host can be seen as precursors of the luminescent Yb-trapped excitons characterized experimentally in the isomorphous SrF(2) crystals.