One-Electron Pseudo-Potential Determination of Stable Isomers of the Li*Ar Excited Clusters: Absorption Spectra

We present pseudo-potential calculations of geometrical structures of stable isomers of LiAr clusters with both an electronic ground state and excited states of the lithium atom. The Li atom is perturbed by argon atoms in LiAr clusters. Its electronic structure obtained as the eigenfunctions of a single-electron operator describing the electron in the field of a Li Ar core, the Li and Ar atoms are replaced by pseudo-potentials. These pseudo-potentials include core-polarization operators to account for the polarization and correlation of the inert core with the valence Lithium electron [J Chem Phys 116, 1839 1]. The geometry optimization of the ground and excited states of LiAr (n = 1-12) clusters is carried out via the Basin-Hopping method of Wales et al. [J Phys Chem 101, 5111 2; J Chem Phys 285, 1368 3]. The geometries of the ground and ionic states of LiAr clusters were used to determine the energy of the high excited states of the neutral LiAr clusters. The variation of the excited state energies of LiAr clusters as a function of the number of argon atoms shows an approximate Rydberg character, corresponding to the picture of an excited electron surrounding an ionic cluster core, is already reached for the 3s state. The result of optical transitions calculations shows that the absorption spectral features are sensitive to isomer structure. It is clearly the case for transitions close to the 2p levels of Li which are distorted by the cluster environment. © 2012 Springer Science+Business Media, LLC.