Spectroscopic Analysis of 1-Butyl-3-methylimidazolium Ionic Liquids: Selection of the Charge Reference and the Electronic Environment

Men, Shuang; Rong, Jingsong; Zhang, Tingting; Wang, Xueting; Lu, Feng; Liu, Chang; Jin, Yujuan

doi:10.1134/s0036024418100308

Cited by 4 publications

(2 citation statements)

References 17 publications

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“…These observations show that the XPS-derived anion-dependent interaction strength scale for ILs is a ground-state effect (in XPS language, an initial-state effect) and not a product of electron density redistribution after the core-hole is created in XPS (i.e., not an XPS final-state effect). This finding strongly backs the assumption used regularly in the IL XPS literature that initial-state effects dominate E B shifts for ILs. − ,− ,− Therefore, the effect of different anions on the cation can be related to ground-state differences.…”

Section: Resultssupporting

confidence: 81%

“…differences can be understood in terms of the ability of electrons surrounding the atom with the core-hole to react to the creation of that core-hole, akin to the polarizability of the neighboring atoms. Almost all experimental XPS studies of ILs have assumed that the initial-state interpretation holds. − ,− Calculated core binding energies, E B (core,calc. ), for a small number of IL ion pairs in the initial-state approximation (without a core-hole) and the final-state approximation (with a core-hole) , gave reasonable matches to experimental data, and comparisons of E B (core,exp.)…”

Section: Introductionmentioning

confidence: 99%

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Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory

Gousseva,

Towers Tompkins,

Seymour

et al. 2024

J. Phys. Chem. B

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Using a combination of experiments and calculations, we have gained new insights into the nature of anion−cation interactions in ionic liquids (ILs). An X-ray photoelectron spectroscopy (XPS)-derived anion-dependent electrostatic interaction strength scale, determined using XPS core-level binding energies for IL cations, is presented here for 39 different anions, with at least 18 new anions included. Linear correlations of experimental XPS core-level binding energies for IL cations with (a) calculated core binding energies (ab initio molecular dynamics (AIMD) simulations were used to generate high-quality model IL structures followed by single-point density functional theory (DFT) to obtain calculated core binding energies), (b) experimental XPS core-level binding energies for IL anions, and (c) other anion-dependent interaction strength scales led to three main conclusions. First, the effect of different anions on the cation can be related to ground-state interactions. Second, the variations of anion-dependent interactions with the identity of the anion are best rationalized in terms of electrostatic interactions and not occupied valence state/unoccupied valence state interactions or polarizability-driven interactions. Therefore, the XPS-derived anion-dependent interaction strength scale can be explained using a simple electrostatic model based on electrostatic site potentials. Third, anion−probe interactions, irrespective of the identity of the probe, are primarily electrostatic, meaning that our electrostatic interaction strength scale captures some inherent, intrinsic property of anions independent of the probe used to measure the interaction strength scale.

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Section: Resultssupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory

Gousseva,

Towers Tompkins,

Seymour

et al. 2024

J. Phys. Chem. B

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Understanding X-ray Photoelectron Spectra of Ionic Liquids: Experiments and Simulations of 1-Butyl-3-methylimidazolium Thiocyanate

et al. 2022

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We demonstrate a combined experimental and computational approach to probe the electronic structure and atomic environment of an ionic liquid, based on core level binding energies. The 1-butyl-3-methylimidazolium thiocyanate [C4C1Im][SCN] ionic liquid was studied using ab initio molecular dynamics, and results were compared against previously published and new experimental X-ray photoelectron spectroscopy (XPS) data. The long-held assumption that initial-state effects in XPS dominate the measured binding energies is proven correct, which validates the established premise that the ground state electronic structure of the ionic liquid can be inferred directly from XPS measurements. A regression model based upon site electrostatic potentials and intramolecular bond lengths is shown to account accurately for variations in core-level binding energies within the ionic liquid, demonstrating the important effect of long-range interactions on the core levels and throwing into question the validity of traditional single ion pair ionic liquid calculations for interpreting XPS data.

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X-ray Photoelectron Spectroscopy of 1-Butyl-2,3-Dimethylimidazolium Ionic Liquids: Charge Correction Methods and Electronic Environment of the Anion

Men

2019

Russ. J. Phys. Chem.

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Spectroscopic Analysis of 1-Butyl-3-methylimidazolium Ionic Liquids: Selection of the Charge Reference and the Electronic Environment

Cited by 4 publications

References 17 publications

Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory

Anion-Dependent Strength Scale of Interactions in Ionic Liquids from X-ray Photoelectron Spectroscopy, Ab Initio Molecular Dynamics, and Density Functional Theory

Understanding X-ray Photoelectron Spectra of Ionic Liquids: Experiments and Simulations of 1-Butyl-3-methylimidazolium Thiocyanate

X-ray Photoelectron Spectroscopy of 1-Butyl-2,3-Dimethylimidazolium Ionic Liquids: Charge Correction Methods and Electronic Environment of the Anion

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