Abstract
The aqueous hydration structure of the Bi3+ion is probed using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) simulations of ion-water clusters and condensed-phase solutions. Anomalous features in the EXAFS spectra are found to be associated with a highly asymmetric first-solvent water shell. The aqueous chemistry and structure of the Bi3+ion are dramatically controlled by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. This leads to a distinct multimodal distribution of water molecules in the first shell that are separated by about 0.2 Å. The lone-pair structure is stabilized by a collective response of multiple waters that are localized near the lone-pair anti-bonding site. The findings indicate that the lone-pair stereochemistry of aqueous Bi3+ions plays a major role in the binding of water and ligands in aqueous solutions.
| Original language | English |
|---|---|
| Pages (from-to) | 14987-14996 |
| Number of pages | 10 |
| Journal | Inorganic Chemistry |
| Volume | 61 |
| Issue number | 38 |
| DOIs | |
| State | Published - Sep 26 2022 |
Funding
R.C.S. and D.C.C. acknowledge the donors of the American Chemical Society Petroleum Research Fund for partial support of this research, as well as the Vice President for Research and Innovation and the College of Engineering of the University of Nevada, Reno. C.I.P and T.G.L. acknowledge support from the Deep Vadose Zone–Applied Field Research Initiative at Pacific Northwest National Laboratory (PNNL). Work by N.G. was supported under project 72685 and that of J.L.F. was supported under project 16248, funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Work by M.B. and D.M.D. was funded by the DOE Office of Science by Argonne National Laboratory (ANL) under Contract No. DE-AC02-06CH11357. This research used resources of the Advanced Photon Source, the U.S. Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Calculations were performed in Pronghorn, the High-Performance Computing cluster of the University of Nevada, Reno, as well as in PNNL Research Computing clusters. This research also benefited from computational resources provided by EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at PNNL. PNNL is operated by Battelle Memorial Institute for the United States Department of Energy under DOE Contract Number DE-AC05-76RL01830. This research also used resources of the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility operated under Contract DE-AC02-05CH11231.