Multipole nuclear shielding factors of hydrogen atom confined by a spherical cavity

Abstract

Nuclear shielding factor is an important quantity to describe the response of an atom under the perturbation of an external field. In this work, we develop the sum-over-states numerical method and the Hylleraas variational perturbation approximation to calculate the multipole nuclear shielding factors for general one-electron systems and apply them to the model of the hydrogen atom confined by a spherical cavity. The generalized pseudospectral method is employed to solve the eigenstates of the unperturbed atom. The obtained dipole nuclear shielding factors are in good agreement with previous calculations and the higher-pole results are reported for the first time. The asymptotic behaviors of the multipole nuclear shielding factors in both the large- and small-confinement limits are analyzed with the assistance of variational perturbation theory. The free-atom values can be exactly reproduced by the second-order perturbation approximation and all multipole nuclear shielding factors in the small-confinement limit tend to zero by a linear law. The variational perturbation method manifests exponential convergence with increasing the order of approximation. The numerical and approximate methods developed in this work together pave the way for further investigation of the multipole nuclear shielding factors for general atomic systems.