PChem Seminar – Brooke Bonar

About the event

Speaker: Brooke Bonar

Group: Peterson Group

Title: Dissociation Energies of the Actinide Halides AnX, An=Ac-Lr and X=F-I, Utilizing Relativistic Composite Coupled Cluster Approaches

Abstract

Relativistic coupled-cluster composite approaches are used to determine the bond dissociation energies (BDEs) of diatomic AnX (X=F, Cl, Br, I) with an expected accuracy of at least 3 kcal/mol, with the motivation of understanding actinide halide bond across the series. This work employes two variants of the Feller-Peterson-Dixon (FPD) 1-3 approach; scalar-based FPD and spinor based FPD. The primary difference between these approaches is the treatment of spin-orbit coupling (SOC), with the former employing a posteriori SOC contributions and the latter including SOC at the orbital level throughout all calculations. Both approaches include contributions associated with basis set incompleteness, outer-core correlation, quantum electrodynamics (QED), and Gaunt. In conjunction with work by Peterson and coworkers, 4 the BDEs determined in this work were used to tailor the ionic and covalent actinide halide bonding models first proposed by Gibson in 2022. 5 These refined models provide insight into the participation of 6d electrons in the actinide halide bond.

References  

1 D. Feller, K. A. Peterson, and D. A. Dixon, J. Chem. Phys. 129 (2008) 204105.

2 D. Feller, K. A. Peterson, and D. A. Dixon, (Elsevier, 2012), pp. 1.

3 D. Feller, K. A. Peterson, and D. A. Dixon, Mol. Phys. 110 (2012) 2381.

4 T. T. Kawagoe, D. M. Merriles, M. D. Morse, and K. A. Peterson, J. Phys. Chem. A 129 (2025) 7842.

5 J. K. Gibson, J. Phys. Chem. A 126 (2022) 272.