Relativistic, nearly basis-set-limit nuclear magnetic shielding constants of the rare gases He–Rn: A way to absolute nuclear magnetic resonance shielding scales

Relativistic four-component ab initio calculations using the Dirac–Coulomb Hamiltonian and converged, very large Gaussian one-particle basis sets are carried out for the nuclear magnetic shielding constants of rare gas atoms He–Rn in their ground state. A discrepancy between two earlier sets of theoretical results for He–Xe is attributed to the basis. Absolute nuclear magnetic resonance shielding scales for the investigated elements are established because electron correlation effects are negligible in this case. Future atomic-beam experiments are discussed.