The physico-chemical properties of the molecules containing actinides are difficult to study both experimentally and theoretically, as their electronic structure is complicated by multireference character of their open f-shell electrons. Large relativistic effects and spin-orbit coupling play an additional role in the complexity of the excited state and optical properties of these species, which may be highly charged. The polarizability of actinide ions effectively alters their interactions with nearby molecules or ligands and is thus of importance to any atomic process where the most diffuse part of the electron density plays a crucial role, including the study of intermolecular forces, scattering phenomena, the optical properties of materials and clusters, charge transfer, and transition moment calculations.  In this work, the polarizabilities have been calculated using the numerical finite field technique in a four-component relativistic framework. Single reference methods like MP2, CCSD, CCSD(T), and multi reference methods including Dirac-Hartree Fock (DHF), Fock-space coupled cluster (FSCC) and Kramers-restricted configuration interaction (KRCI) have been performed in order to account for electron correlation effects. Comparisons between polarizabilities calculated using DHF, FSCC, KRCI methods have been made.  In addition to the ground state, this study also reports the polarizability data for the first two excited states of U3+/4+, Np3+/4+ and Pu3+/4+ ions at different levels of theory. The parallel component of the dipole polarizability has been calculated for AnO2+/2+ (An=U, Np, Pu).

Accurate dipole polarizabilities for actinides in the III-VI oxidation states

248th National Meeting (2014)

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