The determination of accurate dipole polarizabilities α and γ for the noble gases

Abstract

The static dipole polarizabilities α and γ for the noble gases helium through xenon have been determined using large flexible one-particle basis sets in conjunction with high-level treatments of electron correlation. The electron correlation methods include single and double excitation coupled-cluster theory (CCSD), an extension of CCSD that includes a perturbational estimate of connected triple excitations, CCSD(T), and second-order perturbation theory (MP2). The computed α and γ values are estimated to be accurate to within a few percent. Agreement with experimental data for the static hyperpolarizability γ is good for neon and xenon, but for argon and krypton the differences are larger than the combined theoretical and experimental uncertainties. Based on our calculations, we suggest that the experimental value of γ for argon is too low. Adjusting this value would also bring the experimental value of γ for krypton into better agreement with our computed result. The MP2 values for the polarizabilities of neon, argon, krypton, and xenon are in reasonable agreement with the CCSD and CCSD(T) values, suggesting that this less expensive method may be useful in studies of polarizabilities for larger systems. © 1991 American Institute of Physics.