Simulations of krypton matrix effects on the electronic spectrum of Na2

A model for calculation of spectral shifts in small molecules due to matrix environments is developed. The approach is based on the one-electron approximation and combines methods of ab initio quantum chemistry, density functional theory, and molecular dynamics simulations. Applications to Na₂Kr₆₂ heteroclusters demonstrate that the model is capable of reproducing spectral shifts of opposite sign for the experimentally studied A–X and B–X transitions in Na₂ trapped inside the Kr matrix.