Zhu Zhaoguo, Marshall Mary, Bowen Kit H, Peterson Kirk A
Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA.
Department of Chemistry, Washington State University, Pullman, Washington 99164, USA.
J Chem Phys. 2022 Feb 7;156(5):054305. doi: 10.1063/5.0079795.
The thorium-gold negative ions ThAu , ThAuO, 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 ThF that is 10 kcal/mol smaller than that of ThAu. The EA values for the Th(IV) species, i.e., ThXO and ThXOH, only differed, however, by 3-4 kcal/mol.
