Molecular polarizabilities as fingerprints of perturbations to water by ions and confinement

Rozsa, Viktor; Pham, Tuan Anh; Galli, Giulia

doi:10.1063/1.5143317

Molecular polarizabilities as fingerprints of perturbations to water by ions and confinement

Journal Article · Wed Mar 25 00:00:00 EDT 2020 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5143317· OSTI ID:1630420

^[1]; Pham, Tuan Anh ^[2]; ^[3]

Univ. of Chicago, IL (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Perturbations to water, both by ions and confining media, have been the focus of numerous experimental and theoretical studies. Yet, several open questions remain, including the extent to which such perturbations modify the structural and dielectric properties of the liquid. Here, we present a first-principles molecular dynamics study of alkali cations in water (Li⁺, Na⁺, and K⁺) as well as of water and LiCl and KCl solutions under confinement within carbon nanotubes (CNTs) of small diameter (1.1-1.5 nm). Our simulations support the view that the water structure is only modified locally in the presence of cations. We found that molecular polarizabilities are fingerprints of hydrogen bonding modifications, which occur at most up to the second solvation shell for all cations in bulk water. Under confinement, we found that the overall value of the molecular polarizability of water molecules near the surface is determined by the balance of two effects, which are quantitatively different in CNTs of different radii: the presence of broken hydrogen bonds at the surface leads to a decrease in the polarizabilities of water molecules, while the interaction with the CNT enhances polarizabilities. Interestingly, the reduction in dipole moments of interfacial water molecules under confinement is instead driven only by changes in the water structure and not by interfacial interactions. As expected, confinement effects on water molecular polarizabilities and dipole moments are more pronounced in the case of the 1.1 nm CNT.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Advanced Materials for Energy-Water Systems (AMEWS). The Center for Enhanced Nanofluidic Transport (CENT); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357; AC52-07NA27344; NA0003864; SC0019112

OSTI ID:: 1630420

Alternate ID(s):: OSTI ID: 1606286
OSTI ID: 1860752

Report Number(s):: LLNL-JRNL-802697; 159580

Journal Information:: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 12 Vol. 152; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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