Are the ground states of the later actinocenes multiconfigurational?:all-electron spin-orbit coupled CASPT2 calculations on An(eta(8)-C8H8)(2) (An = Th, U, Pu, Cm)

Kerridge, Andrew and Kaltsoyannis, Nikolas (2009) Are the ground states of the later actinocenes multiconfigurational?:all-electron spin-orbit coupled CASPT2 calculations on An(eta(8)-C8H8)(2) (An = Th, U, Pu, Cm). Journal of Physical Chemistry A, 113 (30). pp. 8737-8745. ISSN 1089-5639

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Abstract

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 (ThCOT2), uranocene (UCOT2), plutonocene (PuCOT2), and curocene (CmCOT2). 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 vertical bar M-J vertical bar = 0, in agreement with its temperature-independent paramagnetism.

Item Type:
Journal Article
Journal or Publication Title:
Journal of Physical Chemistry A
Uncontrolled Keywords:
/dk/atira/pure/subjectarea/asjc/1600/1606
Subjects:
ID Code:
71572
Deposited By:
Deposited On:
03 Nov 2014 14:16
Refereed?:
Yes
Published?:
Published
Last Modified:
25 Mar 2020 04:34