Journal of Physical Chemistry A, Vol.113, No.45, 12626-12631, 2009
Assessment of the Accuracy of Shape-Consistent Relativistic Effective Core Potentials Using Multireference Spin-Orbit Configuration Interaction Singles and Doubles Calculations of the Ground and Low-Lying Excited States of U4+ and U5+
Multireference spin-orbit configuration interaction calculations were used to determine the accuracy of 60-, 68, and 78-electron shape-consistent relativistic effective core potentials (RECPs) for uranium V and VI ground and low-lying excited states. Both 5f(n) and (5f6d)(n), (n = 1, 2) reference spaces were investigated using correlation-consistent double-zeta quality basis sets. Accuracy was assessed against gas-phase experimental spectra. The 68-electron RECP calculations yielded low relative and rms errors and predicted the empirical ordering of states most consistently.