Binding of Sulfates and Water to Monovalent Cations

Stevens, Mark J.; Rempe, Susan B.

doi:10.1021/acs.jpca.4c05454

Binding of Sulfates and Water to Monovalent Cations

Journal Article · Thu Dec 05 23:00:00 EST 2024 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.4c05454· OSTI ID:2530838

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Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies

The binding of the sulfate ligand group to monovalent cations in the presence of water is important for many systems. To understand the structure and energetics of sulfate complexes, we use density functional theory to study ethyl sulfate binding to the monovalent cations Li⁺, Na⁺, and K⁺, and to water. The free energies of binding and optimal structures are calculated for a range of the number of ethyl sulfates and waters. Without water, the most optimal structure for all the cations is bidentate binding by two ethyl sulfates, yielding a 4-fold coordination. With water, the lowest free energy structures also have two ethyl sulfates, but the coordination varies with cations. For complexes with water, the four oxygen atoms in the sulfate group enable multiple binding geometries for the cations and for hydrogen bonding with water. Many of these geometries differ in free energy by only a small amount (1–2 kcal/mol), meaning there will be multiple binding configurations in bulk solution. In comparison to the optimal structures for binding to the carboxylate group, there is more variation for binding to the sulfate group as a function of cation type and the number of waters. Further, the polarization of the atoms is significant and varies among the sulfate oxygen atoms. The water oxygen charge is often larger than that of sulfate oxygen, which plays a role in the preference for monodentate ligand binding to cations in the presence of water.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: NA0003525

OSTI ID:: 2530838

Report Number(s):: SAND--2025-02983J

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 50 Vol. 128; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Binding of Sulfates and Water to Monovalent Cations

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