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

Kód výsledku v 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>

Výsledek na webu

<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>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

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

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

—

Svazek periodika

150

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

164702-1 - 164702-13

Kód UT WoS článku

000466698700047

EID výsledku v databázi Scopus

2-s2.0-85064988219