Experimental and Theoretical Investigations of Solvation Dynamics of Ionic Fluids:  Appropriateness of Dielectric Theory and the Role of DC Conductivity

Halder, Mintu; Headley, L. Sanders; Mukherjee, Prasun; Song, Xueyu; Petrich, Jacob W.

doi:10.1021/jp062936l

Cited by 72 publications

(138 citation statements)

References 38 publications

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“…23- 25 Here we compare the micellar system formed by 1-cetyl-3-vinylimida- A typical instrument response function is shown. The decay at blue end of the spectrum decays faster than that of at the red end of the spectrum.…”

Section: Discussionmentioning

confidence: 99%

“…[33][34][35][36] Major questions regarding dynamic solvation by ionic liquids deal with whether the organic cation or the inorganic anion solvate preferentially on different time scales, the role of the correlated motion of the ion pairs and their lifetime, and the importance of translational motion of the ions relative to dipolar relaxation. [23][24][25] Here, we attempt to address some of these questions by studying the solvation of the dye, coumarin 153, in a bulk ionic liquid and its corresponding micelle in water ( Figure 1). Because coumarin 153 is only sparingly soluble and weakly fluorescent in water, a clear distinction can be made between its fluorescent properties in the bulk ionic liquid and that in the micelles formed from the ionic liquid.…”

Section: Introductionmentioning

confidence: 99%

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Assessing the Roles of the Constituents of Ionic Liquids in Dynamic Solvation: Comparison of an Ionic Liquid in Micellar and Bulk Form

et al. 2006

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Dynamic solvation of the dye, coumarin 153, is compared in an ionic liquid that forms micelles in water against the bulk solvent. This provides the unprecedented opportunity of investigating the behavior of the ionic liquid in two globally different configurations. It is proposed that the imidazolium moiety is in both cases responsible for the majority of the solvation, which manifests itself in the first 100 ps. Exploiting the use of ionic liquids capable of accommodating specific structures thus provides a deeper insight into how solutes interact with these fascinating and interesting solvents (at least those that are imidazolium based) that are gaining ever increasing interest in the scientific community.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Assessing the Roles of the Constituents of Ionic Liquids in Dynamic Solvation: Comparison of an Ionic Liquid in Micellar and Bulk Form

et al. 2006

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“…We demonstrated a direct pH measurement in EAN by using an ion selective field effect transistor (IS-FET) electrode [22]. Moreover, dynamic properties such as a dielectric spectroscopy [23] and solvation dynamics of EAN ionic liquid [24,25] have also been reported. For further understanding of both static and dynamic properties of EAN as liquid and/or solvent, it is indispensable to elucidate the liquid structure of EAN at a molecular level.…”

Section: Introductionmentioning

confidence: 99%

Liquid Structure and the Ion-Ion Interactions of Ethylammonium Nitrate Ionic Liquid Studied by Large Angle X-Ray Scattering and Molecular Dynamics Simulations

Umebayashi

Chung

Mitsugi

et al. 2008

J. Comput. Chem. Jpn.

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Room temperature ionic liquids (RTILs) are useful as new solvents or materials owing to their favorable properties such as negligible vapor pressure, non-flammability, and wide electrochemical window. For further development of new RTILs, it is indispensable to understand macroscopic properties as solvent and/or liquids of RTILs at a molecular or atomistic level. Here, liquid structure and the ion-ion interactions of room temperature ionic liquid ethylammonium nitrate (EAN) were studied by means of large angle X-ray scattering (LAXS) experiment and molecular dynamics simulations. X-ray interference function for EAN shows a small peak of 0.62Å -1 indicating nano-scale segregation in the ionic liquid. X-ray radial distribution function as the form of D(r) -4πr 2 ρ 0 evidently shows a peak of 3.4 and broad ones of 4.7, 8 and 12Å, suggesting that EAN has long range ordering in the liquid state. The intra-molecular X-ray interference function was estimated on the basis of molecular geometries found in crystals to yield the inter-molecular X-ray pair correlation function G LAXS inter (r). In G LAXS inter (r), peaks of 3.0, 3.4, and 4.7Å were found as the atom-atom correlation. The peak of 3.0Å can be assigned to the atom-atom correlation of N (C 2 H 5 NH 3 + ) O (NO 3 -) in the NH O hydrogen bonding. In addition, the peak of 3.4Å is also ascribable to C (C 2 H 5 NH 3 + ) O (NO 3 -) correlations in the CH O interactions. Molecular dynamics simulations based on newly developed force fields to describe a series of primary ammonium cation were performed to ascribe the peaks found in G LAXS inter (r). The X-ray interference function i MD (s) and the pair correlation function G MD (r) derived from simulations were reasonably in agreement with the experimental ones. According to the partial atom-atom correlation functions derived from the simulations, the experimentally observed peaks of 3.0 and 3.4Å can be ascribable to the NH O and the CH O correlations in the closest ethylammonium and nitrate interaction, respectively. The CH O interactions may play an important role in macroscopic properties of this kind of ionic liquids.

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“…35 Major questions regarding dynamic solvation by ionic liquids deal with whether the organic cation or the inorganic anion solvates preferentially on different time scales, the role of the correlated motion of the ion pairs and their lifetime, and the importance of translational motion of the ions relative to dipolar relaxation. [23][24][25] Previously, we attempted to address some of these questions by studying the solvation of the dye coumarin 153 in a bulk imidazolium ionic liquid, 1-cetyl-3-vinylimidazolium bromide ([CVIM + ][Br -]), and its corresponding micelle in water. 36 (There is a growing body of work on the subject of ionic liquids in micelles, microemulsions, and related systems.…”

Section: Introductionmentioning

confidence: 99%

Dynamic Solvation in Phosphonium Ionic Liquids: Comparison of Bulk and Micellar Systems and Considerations for the Construction of the Solvation Correlation Function, C(t)

et al. 2008

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Dynamic solvation of the dye coumarin 153 is studied in a phosphonium ionic liquid: hexadecyltributylphosphonium bromide, [(C4)3C16P+][Br-]. It forms micelles in water, and the bulk also exists as a liquid under our experimental conditions. This system permits a comparison with an imidazolium ionic liquid studied earlier, which also formed micelles in water (J. Phys. Chem. A 2006, 110, 10725−10730). We conclude that our analysis of the comparable situation in a phosphonium liquid is not as definitive as we had proposed earlier, i.e., that the majority of the early-time solvation arises from the organic cation. Part of the difficulty in performing this analysis is most likely due to the amount of water that is associated with the micelle. In the course of this work, we have focused on the calculation of the solvation correlation function, C(t), and investigated how it depends upon the methods with which the "zero-time" spectrum is constructed. Arlington, Box 19065, Arlington, Texas 76019 ReceiVed: NoVember 8, 2007; In Final Form: December 7, 2007 Dynamic solvation of the dye coumarin 153 is studied in a phosphonium ionic liquid: hexadecyltributylphosphonium bromide, [(C 4 ) 3 C 16 P + ][Br -]. It forms micelles in water, and the bulk also exists as a liquid under our experimental conditions. This system permits a comparison with an imidazolium ionic liquid studied earlier, which also formed micelles in water (J. Phys. Chem. A 2006, 110, 10725-10730). We conclude that our analysis of the comparable situation in a phosphonium liquid is not as definitive as we had proposed earlier, i.e., that the majority of the early-time solvation arises from the organic cation. Part of the difficulty in performing this analysis is most likely due to the amount of water that is associated with the micelle. In the course of this work, we have focused on the calculation of the solvation correlation function, C(t), and investigated how it depends upon the methods with which the "zero-time" spectrum is constructed. Keywords

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Experimental and Theoretical Investigations of Solvation Dynamics of Ionic Fluids: Appropriateness of Dielectric Theory and the Role of DC Conductivity

Cited by 72 publications

References 38 publications

Assessing the Roles of the Constituents of Ionic Liquids in Dynamic Solvation: Comparison of an Ionic Liquid in Micellar and Bulk Form

Assessing the Roles of the Constituents of Ionic Liquids in Dynamic Solvation: Comparison of an Ionic Liquid in Micellar and Bulk Form

Liquid Structure and the Ion-Ion Interactions of Ethylammonium Nitrate Ionic Liquid Studied by Large Angle X-Ray Scattering and Molecular Dynamics Simulations

Dynamic Solvation in Phosphonium Ionic Liquids: Comparison of Bulk and Micellar Systems and Considerations for the Construction of the Solvation Correlation Function, C(t)

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