Journal of Chemical Physics, Vol.103, No.22, 9692-9704, 1995
Electronic-Structure and Electric Properties of the Alkali-Metal Dimers
Dipole moments and dipole polarizabilities of a series of the alkali metal atom dimers involving Li, Na, K, acid Rb are calculated at the level of different coupled cluster approximations as well as the complete active space self-consistent-held approach followed by the perturbation treatment of the dynamical correlation effects. All reported calculations have been carried out with recently developed polarized basis sets. The electron correlation effects on these electric properties are studied within the valence and valence plus next-to-valence shell approximations. Also the relativistic contribution is calculated by using the quasirelativistic scalar (mass-velocity+Darwin terms) approximation. A comparison of results of different methods indicates that the values calculated by the coupled clusters method in which one- and two-electron clusters are treated iteratively and the three-body terms perturbatively [as defined in the CCSD(T) method] are well saturated in terms of the electron correlation contribution to molecular electric properties of the dimers. The achieved agreement with available experimental data is for most molecules fairly good. The interpretation of the electric property data is based on the analysis of the valence and core-polarization contributions and the observed regularities are elucidated in terms of simple molecular orbital ideas. The dipole moments of the heteronuclear dimers follow the pattern predicted by electronegativities of the two atoms. The perpendicular component of the electric dipole polarizability has been found to mostly reflect its atomlike origin, while the parallel one is intimately related to the electronic structure of the week bonding in the dimers, The relativistic effect becomes of certain importance only for the rubidium compounds. The results of our calculations are compared with ab initio and empirical pseudopotential data and with more recent calculations using the density functional theory methods. Our results indicate that the density functional methods lead to fairly reliable polarizability data, though they depend on the choice of the exchange and exchange-correlation potentials.
Keywords:LASER-INDUCED FLUORESCENCE;LEVEL-CORRELATED CALCULATIONS;2ND-ORDER PERTURBATION-THEORY;CORE POLARIZATION POTENTIALS;GROUND-STATE PROPERTIES;DIPOLE POLARIZABILITIES;MOLECULAR POLARIZABILITIES;ABINITIO CALCULATIONS;BASIS-SETS;MB-RSPT