Theoretical Study of Pu and Am Tetracarbide Molecules

摘要

The electronic structure and ground-state molecular properties of Pu and Am tetracarbides have been investigated by relativistic multireference calculations using CASSCF/CASPT2 theory as well as by density functional theory in conjunction with relativistic pseudopotentials. The CASSCF/CASPT2 treatment has been extended by spin–orbit coupling effects for selected species using the CAS state-interaction method. The five atoms can form various structural isomers, from which 12 ones have been identified in our study. The electronic ground state in both molecules corresponds to a planar fan-type structure of C_(2v) symmetry, in which the actinide atom is connected to a bent C_4 moiety. The other structures are much higher in energy, the ones computed in this study appear between 250 and 1050 kJ/mol. The bonding characteristics in the most relevant structures have been analyzed on the basis of the valence molecular orbitals and natural bond orbital analysis. The most stable structures have been characterized by their spectroscopic (vibrational and electron) properties.