A theoretical study of the spectral shifts of Xe atom in Ar environment

•Combining statistical mechanics and quantum mechanics to successfully describe the spectral properties of Xe in liquid Ar.•Calculations of the electronic transitions of the Xe (S1→P1, P3) atom in explicit Ar environment.•A systematic study of the low-lying electronically excited states of rare-gas liquid.•The spectral shifts are analyzed for different thermodynamic conditions, including supercritical.

Liquid configurations generated by Metropolis Monte Carlo simulations are used in time-dependent density functional theory calculations of the spectral line shifts of atomic impurities in rare-gas environment. Consistent results are obtained for the Xe 5p→6s5p→6s excitation in Ar environment in all thermodynamic conditions considered, with densities varying from 0.15 to 1.40 g/cm31.40 g/cm3, thus ranging from the low to the high-density situation, including supercritical condition. The results reproduce very well the dependence of the spectral shift with the density, giving also good quantitative results for the low, intermediate and high-density cases.

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