Single-Particle Dynamics at the Intrinsic Surface of Aqueous Alkali Halide Solutions

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F21%3A43923306" target="_blank" >RIV/60461373:22340/21:43923306 - isvavai.cz</a>

Result on the web

<a href="https://pubs.acs.org/doi/10.1021/acs.jpcb.0c09989" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpcb.0c09989</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcb.0c09989" target="_blank" >10.1021/acs.jpcb.0c09989</a>

Result language

angličtina

Original language name

Single-Particle Dynamics at the Intrinsic Surface of Aqueous Alkali Halide Solutions

Original language description

The distribution of ions in the proximity of the liquid-vapor interface of their aqueous solution has been the subject of an intense debate during the last decade. The effects of ionic polarizability have been one of its salient aspects. Much less has been said about the corresponding dynamical properties, which are substantially unexplored. Here, we investigate the single-particle dynamics at the liquid-vapor interface of several alkali halide solutions, using molecular dynamics simulations with polarizable and nonpolarizable force fields and intrinsic surface analysis. We analyze the diffusion coefficient, residence time, and velocity autocorrelation function of water and ions and investigate how these properties depend on the molecular layer where they reside. While anions are found in the first molecular layer for relatively long times, cations are only making quick excursions into it, thanks to thermal fluctuations. The in-layer residence time of ions and their molar fraction in the layer turned out to be linearly dependent on each other. We interpret this unexpected result using a simple two-state model. In addition, we found that, unlike water and other neat molecular liquids that show a different diffusion mechanism at the surface than in the bulk of their liquid phase, ions do not enjoy enhanced mobility in the surface layer of their aqueous solution. This result indicates that ions in the surface layer are shielded by their nearest water neighbors from being exposed to the vapor phase as much as possible. Such positions are available for the ions at the negatively curved troughs of the molecularly rugged liquid surface. © 2021 American Chemical Society.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA18-16577S" target="_blank" >GA18-16577S: Droplets, ice and aerosols in silico: Combining ab initio and classical approaches</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2021

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Physical Chemistry B

ISSN

1520-6106

e-ISSN

—

Volume of the periodical

125

Issue of the periodical within the volume

2

Country of publishing house

US - UNITED STATES

Number of pages

15

Pages from-to

665-679

UT code for WoS article

000613197600018

EID of the result in the Scopus database

2-s2.0-85099952740