Carbon monoxide activation by atomic thorium: ground and excited state reaction pathways.

ABSTRACT

Multi-reference configuration interaction (MRCI) and single reference coupled cluster calculations are performed for the ThCO and OThC isomers. Scalar and spin-orbit relativistic effects are considered through a relativistic pseudopotential and the coupling of MRCI wavefunctions via the Breit-Pauli spin-orbit Hamiltonian. Optimized geometries, excitation energies, and vibrational frequencies are reported for both isomers. Full potential energy profiles are constructed for the Th+CO reaction and the conversion of the produced ThCO to OThC. Linear ThCO was found to be more stable than the highly ionic bent OThC system by about 4 kcal mol-1. The interconversion barrier is estimated to be around 30 kcal mol-1. Our results are in agreement with earlier experimental data for the two isomers. The lowest lying states of Th do not populate f-orbitals and resemble the electronic structure of Ti. Therefore, the ability of the two atoms to activate the C[triple bond, length as m-dash]O bond is compared. OTiC is found to be about 40 kcal mol-1 less stable than TiCO revealing the efficiency of Th and possibly other f-block elements to activate multiple chemical bonds as opposed to d-block metals.