The size of the cations (either Ca2+, Sr2+, Ga+, or Au+) at the FA1-type color centers on the (100) surface of LiCl crystal plays an important role in the optical properties of this surface. In this work, double-well potentials at this surface were investigated using ab initio quantum mechanical methods. Quantum clusters were embedded in simulated Coulomb fields that closely approximate the Madelung fields of the host surface, and the ions that were the nearest neighbors to the FA1 site were allowed to relax to equilibrium. The calculated Stokes-shifted optical transition bands, optical–optical conversion efficiency, and relaxed excited states of the defect-containing surface, as well as the orientational destruction of the color centers, recording sensitivity, exciton (energy) transfer, and the Glasner–Tompkins empirical relation were all found to be sensitive to the size of the dopant cation.