ThAu2–, ThAu2O–, and ThAuOH– anions: Photoelectron spectroscopic and theoretical characterization

Zhu, Zhaoguo; Marshall, Mary; Bowen, Kit H.; Peterson, Kirk A.

doi:10.1063/5.0079795

Title: ThAu₂^–, ThAu₂O^–, and ThAuOH^– anions: Photoelectron spectroscopic and theoretical characterization

Journal Article · 06 February 2022 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/5.0079795 · OSTI ID:1909828

Zhu, Zhaoguo ^[1]; Marshall, Mary ^[2];

^[2];

^[3]

Johns Hopkins Univ., Baltimore, MD (United States); The Johns Hopkins University
Johns Hopkins Univ., Baltimore, MD (United States)
Washington State Univ., Pullman, WA (United States)

The thorium–gold negative ions ThAu₂^–, ThAu₂O^–, and ThAuOH^– have been observed and experimentally characterized by anion photoelectron spectroscopy. These experiments are accompanied by extensive ab initio electronic structure calculations using a relativistic composite methodology based primarily on coupled cluster singles and doubles with perturbative triples calculations. The theoretical electron affinities (EAs) at 0 K agree with the experimental adiabatic EAs to within 0.02 eV for all species. Two separate isomers were located in the calculations for ThAuOH^–, and detachment from both of these appears to be present in the photoelectron spectrum. Excited electronic states of the neutral molecules are reported at the equation of motion-coupled cluster singles and doubles level of theory. Atomization energies and heats of formation are also calculated for each neutral species and have expected uncertainties of 3 and 4 kcal/mol, respectively. The σ bonds between Th and Au are determined by natural bond orbital analysis to consist of predominately sd hybrids on Th bonding with the Au 6s orbital. In order to investigate the correspondence between the bonding in Th–Au and Th–F molecules, a limited number of calculations were also carried out on most of the F-analogs of this study. These results demonstrate that Au does behave like F in these cases, although the Th–F σ bonds are much more ionic compared to Th–Au. This results in an EA for ThF₂ that is 10 kcal/mol smaller than that of ThAu₂. The EA values for the Th(IV) species, i.e., ThX₂O and ThXOH, only differed, however, by 3–4 kcal/mol.

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Research Organization:: Johns Hopkins Univ., Baltimore, MD (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0008501; SC0019317

OSTI ID:: 1909828

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 5 Vol. 156; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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