Ion Solvation and Transport in Narrow Carbon Nanotubes: Effects of Polarizability, Cation-π Interaction, and Confinement

Aydin, Fikret; Moradzadeh, Alireza; Bilodeau, Camille L.; Lau, Edmond Y.; Schwegler, Eric; Aluru, Narayana R.; Pham, Tuan Anh

doi:10.1021/acs.jctc.0c00827

Ion Solvation and Transport in Narrow Carbon Nanotubes: Effects of Polarizability, Cation-π Interaction, and Confinement

Journal Article · Wed Feb 24 00:00:00 EST 2021 · Journal of Chemical Theory and Computation

DOI:https://doi.org/10.1021/acs.jctc.0c00827· OSTI ID:1798034

^[1]; ^[2]; ^[3]; Lau, Edmond Y. ^[1]; Schwegler, Eric ^[1]; ^[2]; ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Illinois at Urbana-Champaign, IL (United States)
Rensselaer Polytechnic Inst., Troy, NY (United States)

Understanding ion solvation and transport under confinement is critical for a wide range of emerging technologies, including water desalination and energy storage. While molecular dynamics (MD) simulations have been widely used to study the behavior of confined ions, considerable deviations between simulation results depending on the specific treatment of intermolecular interactions remain. In the following, we present a systematic investigation of the structure and dynamics of two representative solutions, that is, KCl and LiCl, confined in narrow carbon nanotubes (CNTs) with a diameter of 1.1 and 1.5 nm, using a combination of first-principles and classical MD simulations. Our simulations show that the inclusion of both polarization and cation-π interactions is essential for the description of ion solvation under confinement, particularly for large ions with weak hydration energies. Beyond the variation in ion solvation, we find that cation-π interactions can significantly influence the transport properties of ions in CNTs, particularly for KCl, where our simulations point to a strong correlation between ion dehydration and diffusion. Finally, our study highlights the complex interplay between nanoconfinement and specific intermolecular interactions that strongly control the solvation and transport properties of ions.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344; SC0019112

OSTI ID:: 1798034

Report Number(s):: LLNL-JRNL--812224; 1019441

Journal Information:: Journal of Chemical Theory and Computation, Journal Name: Journal of Chemical Theory and Computation Journal Issue: 3 Vol. 17; ISSN 1549-9618

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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Ion Solvation and Transport in Narrow Carbon Nanotubes: Effects of Polarizability, Cation-π Interaction, and Confinement

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