Theoretical study of spectroscopical properties of Na and Na-2 in argon clusters and matrices

摘要

We present a calculation of the structure and the optical transitions of sodium atoms and dimers embedded in argon clusters and matrices. We studied several different systems: A single sodium atom in a dodecahedral argon cluster, a Na atom in a substitutional site of a fcc (face-centered-cubic) Ar lattice containing 63 atoms and a sodium dimer in a 9-atom vacancy of the same fee lattice (Na-2@Ar-54). For optimizing the system geometry in its ground state, we use a simplified tight-binding scheme of a metal cluster dressed by the metal-matrix and matrix-matrix van der Waals interactions. A procedure closer to ab initio methodology is then applied using e-Na+ and e-Ar semi-local pseudopotentials and core-polarization operators to determine the electronic structure of the metal valence electrons in the environment of the rare-gas atoms. The electronic transitions and oscillator strengths are obtained by a full two-electron configuration interaction (CI) treatment in the case of Na-2@Ar-54. The A(1) Sigma(u)(+) --> X-1 Sigma(g)(+) transition is redshifted in comparison to the free Na-2 dimer. This phenomenon does not appear in the case of a matrix-isolated atom, where all lines are blueshifted. (C) 1998 American Institute of Physics. [References: 43]