2009/07/02 by Andrew Kerridge, Nikolas Kaltsoyannis · 1 citation
Chemistry · Physics and Astronomy · #Radioactive element chemistry and processing #Advanced Chemical Physics Studies #Organometallic Complex Synthesis and Catalysis
paper · doi:10.1021/jp903912q
openalex publication_date 2009/07/02 · openalex created_date 2016/06/24 · openalex updated_date 2026/07/07
Spin-orbit free and spin-orbit coupled CASPT2 wave functions and energies are presented for the ground and low-lying excited states of four actinide element sandwich molecules; thorocene (ThCOT(2)), uranocene (UCOT(2)), plutonocene (PuCOT(2)), and curocene (CmCOT(2)). Spin-orbit coupling is found to make little difference to the equilibrium geometry of uranocene and plutonocene but has a significant effect on the energy spectrum of all the systems considered here other than thorocene. In all cases, however, the spin-orbit free ground states make the dominant contribution to their spin-orbit coupled counterparts. Following work presented in J. Phys. Chem. A 2009, 113, 2896, the variation in the multiconfigurational character of the ground-state wave functions as the 5f series is crossed is quantified via the occupation of the a(u)/b(1u) (e(2u)) metal-ring bonding and antibonding natural orbitals. The ground state of plutonocene is found to be nondegenerate with |M(J)| = 0, in agreement with its temperature-independent paramagnetism.