Polarizabilities of neutral atoms and atomic ions with a noble gas electron configuration

Abstract

Atomic polarizabilities play an important role in the development of force fields for molecular simulations, as well as for the development of qualitative concepts of atomic and molecular behavior. Coupled cluster theory at the coupled cluster singles doubles triples level with very large correlation-consistent basis sets with extended diffuse functions has been used to predict the polarizabilities of the atomic neutrals, mono-cations and mono-anions with a noble gas configuration. Additional corrections for scalar relativistic and spin-orbit effects were also included for the electron configurations of Kr, Xe, and Rn. The results are in excellent agreement with experiment or with other high level calculations where available. The current results for most of these species represent the best available values for the polarizabilities. The results show that the polarizability of H- is very difficult to calculate without extremely diffuse functions. The polarizability of H- is the largest value, 34.05 Å3, calculated for all species in the current study. The polarizabilities of the remaining halogen anions are also the best available values. The polarizabilities of the halogen anions (excluding F-) and H- have a linear correlation with the electron affinity of the neutral atom. Spin-orbit effects, even for closed shell species, cannot be ignored for quantitative accuracy, and the inclusion of spin-orbit effects for Fr+, Rn, and At- increases the polarizability by 4%, 6%, and 15%, respectively.