Water Defect Stabilizes the Bi3+ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure

Driscoll, Darren M.; Shiery, Richard C.; D’Annunzio, Nicolas; Boglaienko, Daria; Balasubramanian, Mahalingam; Levitskaia, Tatiana G.; Pearce, Carolyn I.; Govind, Niranjan; Cantu, David C.; Fulton, John L.

doi:10.1021/acs.inorgchem.2c01693

Title: Water Defect Stabilizes the Bi³⁺ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure

Journal Article · 12 September 2022 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.2c01693 · OSTI ID:1893143

^[1]; Shiery, Richard C. ^[2]; D’Annunzio, Nicolas ^[3]; Boglaienko, Daria ^[3];

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Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
University of Nevada, Reno, NV (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

In this work, the aqueous hydration structure of Bi³⁺ 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 of 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 is dramatically controlled by the water stabilization of a lone-pair electronic state involving the mixed 6s and 6p orbitals. This leads to a distinct multi-modal distribution of waters in the first shell that are separated by about 0.2Å. 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⁺ plays a major role in the binding of water and ligands in aqueous solutions.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Argonne National Laboratory (ANL), Lemont, IL (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; AC05-76RL01830

OSTI ID:: 1893143

Report Number(s):: PNNL-SA-170091

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 38 Vol. 61; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Water Defect Stabilizes the Bi³⁺ Lone-Pair Electronic State Leading to an Unusual Aqueous Hydration Structure