Direct Correlation between Ionic Liquid Transport Properties and Ion Pair Lifetimes: A Molecular Dynamics Study

被引：223

作者：

Zhang, Yong ^{[1
]}

Maginn, Edward J. ^{[1
]}

机构：

[1] Univ Notre Dame, Dept Chem & Biomol Engn, Notre Dame, IN 46556 USA

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2015年 / 6卷 / 04期

基金：

美国国家科学基金会;

关键词：

ALKYL CHAIN; TEMPERATURE; CONDUCTIVITY; SIMULATION; CATIONS;

D O I：

10.1021/acs.jpclett.5b00003

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Self-diffusivities as a function of temperature were computed for 29 different ionic liquids (ILs) covering a wide variety of cation and anion classes. Ideal ionic conductivities (sigma(NE)) were estimated from the self-diffusivities via the Nernst-Einstein relation. The ion pair (IP) lifetimes (tau(IP)) and ion cage (IC) lifetimes (tau(IC)) of each IL were also computed. A linear relationship between the calculated self-diffusivities and the inverse of IP or IC lifetimes was observed. A similar inverse linear relationship was also observed for ideal ionic conductivity. These relationships were found to be independent of temperature and the nature of the IL. These observations connect macroscopic dynamic properties with local atomic-level motions and strongly suggest that the dynamics of ILs are governed by a universal IP or IC forming and breaking mechanism. Thus, in order to design an ionic liquid with enhanced dynamics, one should consider how to minimize IP or IC lifetimes.

引用

页码：700 / 705

页数：6

共 36 条

[1] Model for the conductivity of ionic liquids based on an infinite dilution of holes [J].

Abbott, AP .

CHEMPHYSCHEM, 2005, 6 (12) :2502-2505

[2] Hydrophobic, highly conductive ambient-temperature molten salts [J].

Bonhote, P ;

Dias, AP ;

Papageorgiou, N ;

Kalyanasundaram, K ;

Gratzel, M .

INORGANIC CHEMISTRY, 1996, 35 (05) :1168-1178

[3] On the structure and dynamics of ionic liquids [J].

Del Pópolo, MG ;

Voth, GA .

JOURNAL OF PHYSICAL CHEMISTRY B, 2004, 108 (05) :1744-1752

[4] Strong, Localized, and Directional Hydrogen Bonds Fluidize Ionic Liquids [J].

Fumino, Koichi ;

Wulf, Alexander ;

Ludwig, Ralf .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (45) :8731-8734

[5] Room temperature ionic liquids of alkylimidazolium cations and fluoroanions [J].

Hagiwara, R ;

Ito, Y .

JOURNAL OF FLUORINE CHEMISTRY, 2000, 105 (02) :221-227

[6] Room-Temperature Ionic Liquids: Solvents for Synthesis and Catalysis. 2 [J].

Hallett, Jason P. ;

Welton, Tom .

CHEMICAL REVIEWS, 2011, 111 (05) :3508-3576

[7] Relations between the Fractional Stokes-Einstein and Nernst-Einstein Equations and Velocity Correlation Coefficients in Ionic Liquids and Molten Salts [J].

Harris, Kenneth R. .

JOURNAL OF PHYSICAL CHEMISTRY B, 2010, 114 (29) :9572-9577

[8] Characterization and comparison of hydrophilic and hydrophobic room temperature ionic liquids incorporating the imidazolium cation [J].

Huddleston, JG ;

Visser, AE ;

Reichert, WM ;

Willauer, HD ;

Broker, GA ;

Rogers, RD .

GREEN CHEMISTRY, 2001, 3 (04) :156-164

[9] Why does a reduction in hydrogen bonding lead to an increase in viscosity for the 1-butyl-2,3-dimethyl-imidazolium-based ionic liquids? [J].

Hunt, Patricia A. .

JOURNAL OF PHYSICAL CHEMISTRY B, 2007, 111 (18) :4844-4853

[10] Performance of Quantum Chemically Derived Charges and Persistence of Ion Cages in Ionic Liquids. A Molecular Dynamics Simulations Study of 1-n-Butyl-3-methylimidazolium Bromide [J].

Kohagen, Miriam ;

Brehm, Martin ;

Thar, Jens ;

Zhao, Wei ;

Mueller-Plathe, Florian ;

Kirchner, Barbara .

JOURNAL OF PHYSICAL CHEMISTRY B, 2011, 115 (04) :693-702

← 1 2 3 4 →