Coupled Cluster Studies of Platinum-Actinide Interactions. Thermochemistry of PtAnOn+ (n = 0-2 and An = U, Np, Pu)

J Phys Chem A. 2021 Jun 24;125(24):5335-5345. doi: 10.1021/acs.jpca.1c03675. Epub 2021 Jun 11.

Abstract

Accurate Pt-An bond dissociation enthalpies (BDEs) for PtAnOn+ (An = U, Np, Pu and n = 0-2) and the corresponding enthalpies for the Pt + OAnOn+ substitution reactions have been studied for the first time using an accurate composite coupled cluster approach. Analogous O-AnOn+ bond dissociation enthalpies are also presented. To make the study possible, new correlation consistent basis sets optimized using the all-electron third-order Douglas-Kroll-Hess (DKH3) scalar relativistic Hamiltonian are developed and reported for Pt and Au, with accompanying benchmark calculations of their atomic ionization potentials to demonstrate the effectiveness of the new basis sets. For the charged PtAnOn+ species (n = 1, 2), a low-spin state (LSS) for which the Pt-An σ bond is doubly occupied is studied together with a high-spin state (HSS) obtained by unpairing the σ bond orbital and placing one electron into the An 5f shell. The relative energies of the two spin states have been compared and qualitatively assessed via natural population and natural bond analyses. The enthalpies for the Pt substitution reactions, i.e., Pt + OAnOn+ → PtAnOn+ + O, are calculated to range from about 14-62 kcal/mol, and the Pt-AnOn+ bond dissociation enthalpies range from about 78-149 kcal/mol for the ground electronic states. For the PtAnO+ species, the LSSs were all predicted to be the ground state, whereas the PtAnO2+ molecules all favored the HSSs. The prediction for PtUO2+ is consistent with previous theoretical findings. The natural bond orbital analyses indicate a triple bond between An and O, with a double to quadruple bond between the An and Pt.