Explicit Solvent Modeling of Solvatochromic Probes in Ionic Liquids: Implications of Solvation Shell Structure

Eilmes, Andrzej; Kubisiak, Piotr

doi:10.1021/acs.jpcb.5b07767

Cited by 10 publications

(8 citation statements)

References 51 publications

(92 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In view of the surprising agreement of gas-phase quantum chemical results with experimental bulk solvent spectra of EMIM-TFSI , and the apparent failure of the implicit solvent model to improve the description of spectral characteristics, we decided to test the explicit approach in computations of EMIM-TFSI IR and UV–vis spectra. The electronic absorption spectrum will be modeled as in our recent work on solvatochromic dyes in ILs, using a sequential approach of classical or ab initio molecular dynamics (AIMD) simulations followed by TD DFT calculations for selected geometries. Vibrational spectra can be successfully obtained from AIMD trajectories via Fourier transform; in this work, we will apply this methodology to the infrared absorption spectrum of EMIM-TFSI liquid.…”

Section: Introductionmentioning

confidence: 99%

Explicit Solvent Modeling of IR and UV–Vis Spectra of 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid

2016

Self Cite

View full text Add to dashboard Cite

Explicit solvent modeling of absorption spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide has been performed. Fourier transform of autocorrelation function of the dipole moment calculated from ab initio molecular dynamics simulations has been used to obtain the IR spectrum of the bulk liquid. A sequential MD/TD DFT procedure has been applied to calculate the UV-vis spectrum. Description of both spectra by explicit solvent model improves with respect to gas phase calculations or implicit solvent with good agreement between computed spectra and the experimental data. The major factor contributing to the improvement has been attributed to better description of structures of cation-anion pairs sampled from molecular dynamics simulations. Ab initio molecular dynamics with Fourier transform has been demonstrated to be a powerful methodology to calculate bulk IR spectra of ionic liquids.

show abstract

Section: Introductionmentioning

confidence: 99%

Explicit Solvent Modeling of IR and UV–Vis Spectra of 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid

2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…They compared the experimental results with the electronic transition energies obtained from time‐dependent density functional theory (TD‐DFT) calculations (TD‐CAM‐B3LYP/aug‐cc‐pVTZ level of theory) and concluded that the absorption spectra in the investigated region is mostly due to the imidazolium cation. Eilmes and co‐workers reported the comparison of experimental and calculated absorption spectra of solvatochromic dyes ( para ‐nitroaniline, N,N ‐diethyl‐ para ‐nitroaniline, and Reichardt's dye) in four ionic liquids: [C 2 C 1 im][BF 4 ], [C 2 C 1 im][Tf 2 N], [C 2 C 1 im][PF 6 ], and [C 2 C 1 im][FSI] . The authors ran MD simulations (both with classical FF and AIMD for [C 2 C 1 im][Tf 2 N]) and used the trajectory to select clusters composed of the probe dye plus a layer of solvating ILs, considering several solvation protocols.…”

Section: Electronic Spectroscopymentioning

confidence: 99%

Computational Spectroscopy of Ionic Liquids for Bulk Structure Elucidation

Saielli

2018

Advcd Theory and Sims

View full text Add to dashboard Cite

Computational spectroscopy" refers to quantum chemistry protocols capable of predicting the electronic and/or magnetic spectra of molecules. The most common techniques used for structural assignment are infrared, electronic, and NMR spectroscopies. Chemists can normally deduce the chemical structure of an unknown substance by using a vast collection of empirical relationships linking the spectral features with the presence or absence of functional groups and, this part mostly by NMR, the connectivity between them and the relative stereochemistry. Computational spectroscopy is a powerful aid for structural elucidation when empirical relationships do not suffice to unambiguously assign the structure. In these cases, the calculated spectrum of a putative structure is compared with the experimental one and the match, or lack thereof, between the two, measured by several statistical parameters, indicates whether or not that structure is the correct one. Is it possible to extend such protocols to bulk phases of complex fluids, such as ionic liquids, rather than covalent molecules, in order to get insights into the average structure of the fluid? It is the aim of this Progress Report to highlight recent advances in this field through the discussion of specific case studies.

show abstract

“…Today there is a large variety of published solvatochromic dyes corresponding to different media, e.g. organic solvents [8,10], ionic liquids [10,11], solvent mixtures [10,[12][13][14][15] or solvent comprising polarity modifiers [16]. What often appears to be challenging is the choice of a suitable solvatochromic probe for the description of a physicochemical problem encompassing solvent polarity effects.…”

Section: Introductionmentioning

confidence: 99%

Probing Solvation Effects in Binary Solvent Mixtures with the Use of Solvatochromic Dyes

Deligkiozi¹,

Papadakis²

2021

Dyes and Pigments - Novel Applications and Waste Treatment

View full text Add to dashboard Cite

In this work three molecules exhibiting dual sensing solvatochromic behaviors are examined in the context of solvation in binary solvent mixtures (BSMs). The compounds studied involve two functional groups with high responsiveness to solvent polarity namely pentacyanoferrate(II) (PC) and azo groups. Two of these compounds are [2]rotaxanes involving alpha- or beta- cyclodextrin (CyD) and the third is their CyD-free precursor. The dual solvatochromic behavior of these compounds is investigated in water/ethlylene glycol (EG) mixtures and their dual solvatochromic responses are assessed in terms of the intensity of solvatochromism and the extent of preferential solvation. To achieve this the linear solvation model by Kamlet, Abboud and Taft [J. Organomet. Chem. 1983, 48, 2877–2887] and the two-phase model of solvation by Bagchi and coworkers [J. Phys. Chem. 1991, 95, 3311–3314] are employed. The influence of the presence or lack of CyD (alpha- or beta-) on these dual solvatochromic sensors is analyzed.

show abstract

Explicit Solvent Modeling of Solvatochromic Probes in Ionic Liquids: Implications of Solvation Shell Structure

Cited by 10 publications

References 51 publications

Explicit Solvent Modeling of IR and UV–Vis Spectra of 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid

Explicit Solvent Modeling of IR and UV–Vis Spectra of 1-Ethyl-3-methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid

Computational Spectroscopy of Ionic Liquids for Bulk Structure Elucidation

Probing Solvation Effects in Binary Solvent Mixtures with the Use of Solvatochromic Dyes

Contact Info

Product

Resources

About