Molecular polarizability in open ensemble simulations of aqueous nanoconfinements under electric field

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F44555601%3A13440%2F19%3A43894624" target="_blank" >RIV/44555601:13440/19:43894624 - isvavai.cz</a>

Result on the web

<a href="https://aip.scitation.org/doi/abs/10.1063/1.5094170" target="_blank" >https://aip.scitation.org/doi/abs/10.1063/1.5094170</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/1.5094170" target="_blank" >10.1063/1.5094170</a>

Result language

angličtina

Original language name

Molecular polarizability in open ensemble simulations of aqueous nanoconfinements under electric field

Original language description

Molecular polarization at aqueous interfaces involves fast degrees of freedom that are often averaged out in atomistic-modeling approaches. The resulting effective interactions depend on a specific environment, making explicit account of molecular polarizability particularly important in solutions with pronounced anisotropic perturbations, including solid/liquid interfaces and external fields. Our work concerns polarizability effects in nanoscale confinements under electric field, open to an unperturbed bulk environment. We model aqueous molecules and ions in hydrophobic pores using the Gaussian-charge-on-spring BK3-AH representation. This involves nontrivial methodology developments in expanded ensemble Monte Carlo simulations for open systems with long-ranged multibody interactions and necessitates further improvements for efficient modeling of polarizable ions. Structural differences between fixed chargeand polarizable models were captured in molecular dynamics simulations for a set of closed systems. Our open ensemble results with the BK3 model in neat aqueous systems capture the 10% reduction of molecular dipoles within the surface layer near the hydrophobic pore walls in analogy to reported quantum mechanical calculations at water/vapor interfaces. The polarizability affects the interfacial dielectric behavior and weakens the electric-field dependence of water absorption at pragmatically relevant porosities. We observe moderate changes in thermodynamic properties and atom and charged-site spatial distributions; the Gaussian distribution of mobile charges on water and ions in the polarizable model shifts the density amplitudes and blurs the charge-layering effects associated with increased ion absorption. The use of polarizable force field indicates an enhanced response of interfacial ion distributions to applied electric field, a feature potentially important for in silk() modeling of electric double layer capacitors. Published under license by AIP Publishing.

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

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Project

—

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2019

Confidentiality

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

Name of the periodical

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

—

Volume of the periodical

150

Issue of the periodical within the volume

16

Country of publishing house

US - UNITED STATES

Number of pages

13

Pages from-to

164702-1 - 164702-13

UT code for WoS article

000466698700047

EID of the result in the Scopus database

2-s2.0-85064988219