Carboxylate binding prefers two cations to one

Stevens, Mark J.; Rempe, Susan B.

doi:10.1039/d2cp03561h

Carboxylate binding prefers two cations to one

Journal Article · Thu Sep 01 00:00:00 EDT 2022 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d2cp03561h· OSTI ID:1894604

Stevens, Mark J. ^[1]; ^[2]

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

Almost all studies of specific ion binding by carboxylates (–COO^-) have considered only a single cation, but clustering of ions and ligands is a common phenomenon. We apply density functional theory to investigate how variations in the number of acetate ligands in binding to two monovalent cations affects ion binding preferences. We study a series of monovalent (Li⁺, Na⁺, K⁺, Cs⁺) ions relevant to experimental work on many topics, including ion channels, battery storage, water purification and solar cells. We find that the preferred optimal structure has 3 acetates except for Cs⁺, which has 2 acetates. The optimal coordination of the cation by the carboxylate O atoms is 4 for both Na⁺ and K⁺, and 3 for Li⁺ and Cs⁺. There is a 4-fold coordination minimum just a few kcal mol^-1 higher than the optimal 3-fold structure for Li+. For two cations, multiple minima occur in the vicinity of the lowest free energy state. Here we find that, for Li, Na and K, the preferred optimal structure with two cations is favored over a mixture of single cation complexes, providing a basis for understanding ionic cluster formation that is relevant for engineering proteins and other materials for rapid, selective ion transport.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: NA0003525

OSTI ID:: 1894604

Alternate ID(s):: OSTI ID: 1886719

Report Number(s):: SAND2022-13374J; 710374

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 36 Vol. 24; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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