Conformations of dimethyl carbonate and its complexes with water: A matrix isolation infrared and ab initio study

Kar, Bishnu Prasad; Ramanathan, N.; Sundararajan, K.; Viswanathan, K. S.

doi:10.1016/j.molstruc.2012.05.007

Cited by 34 publications

(25 citation statements)

References 30 publications

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“…Matrix isolation experiments were performed using a Sumitomo closed cycle helium compressor-cooled cryostat (HC-4E1) to attain a temperature of 12 K. The experimental details have been described elsewhere [17][18][19][20][21].…”

Section: Methodsmentioning

confidence: 99%

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Does a hydrogen bonded complex with dual contacts show synergism? A matrix isolation infrared and ab-initio study of propargyl alcohol–water complex

Saini

Viswanathan

2016

Journal of Molecular Structure

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Section: Methodsmentioning

confidence: 99%

“…No study exists on this molecule using matrix isolation spectroscopy, a technique ideally suited for the study of conformations [17,18]. Ab initio computations were performed to obtain the structures of the conformers and their vibrational features.…”

Section: H 3 þC 3 H 3 /C 6 H 6 /Pah/sootmentioning

confidence: 99%

Does a hydrogen bonded complex with dual contacts show synergism? A matrix isolation infrared and ab-initio study of propargyl alcohol–water complex

Saini

Viswanathan

2016

Journal of Molecular Structure

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“…These substitutions had small effects on the HOMO and LUMO energies but increased the dipole moment of the solvated lithium ion considerably. 39 This suggests that DMC can help the The Journal of Physical Chemistry C Article net solvation by making the primary coordinated ion more polar, which then can increase the attraction of the second solvation sphere. Also note that in the mixed solvated species, the aa-DMC conformation is the lower energy species.…”

Section: Articlementioning

confidence: 99%

Role of Mixed Solvation and Ion Pairing in the Solution Structure of Lithium Ion Battery Electrolytes

et al. 2015

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The solution structures of organic carbonate solvents (ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and diethyl carbonate (DEC)) as electrolyte solutions of LiPF 6 were investigated with FTIR and NMR spectroscopy and DFT computational methods. Both coordinated and uncoordinated solvents are observed by IR spectroscopy, allowing the determination of solvent coordination numbers, which a range from 2 to 5. The predominant species in solution changes as a function of LiPF 6 concentration. At low salt concentrations (<1.2 M), the predominant species is a solvent-separated ion pair, whereas at high salt concentrations (>2.0 M) the predominant species in solution is the contact ion pair. In mixed solvent systems (PC−DMC, PC−DEC, EC−DMC, or EC−DEC), the mixed solvated cations are observed in the presence of high concentrations of uncoordinated cyclic carbonate despite the much larger dielectric constant of the cyclic carbonates than dielectric constant of linear carbonate.

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“…The negative-going bands present in all of the spectra correspond to most of the vibrational modes of species belonging to the electrolyte, indicating the formation of a homogeneous, well-covering thin fi lm at the electrode surface during electrochemical cycling. [ 37,38,[48][49][50] A large number of studies were dedicated to characterize electrolyte properties and the resulting SEI layer. The right-hand frame in Figure 2 shows the high-wavenumber region with a different absorbance scale (enlarged by a factor of six).…”

Section: Sei Formation In Lipf 6 -Based Electrolyte Containing Vc Andmentioning

confidence: 99%

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Corte

Caillon

Jordy

et al. 2015

Advanced Energy Materials

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special environment for its characterization appear as steps which in most cases might strongly modify the active material. [ 1 ] Benefi ting from characterization techniques able to analyze the electrodes in situ and in operando therefore appears of uttermost importance for obtaining information of direct relevance regarding the electrode processes. We show in the present work that such pieces of information can be obtained by using in situ Fourier-transform infrared (FTIR) spectroscopy in a suitable geometry, which avoids the traditional limitations associated with this technique and allows for quantitative information to be extracted. [ 2 ] This approach therefore brings significant complementary information to other useful techniques operating in the electrochemical environment, which focus either on electrode materials, such as nuclear magnetic resonance (NMR) [ 3,4 ] or X-ray absorption, diffraction or imaging, [ 5,6 ] or on electrode surfaces, such as scanning probe microscopies. [ 7,8 ] Using infrared spectroscopy at the electrochemical interface has already been attempted in the context of the study of battery electrodes. [9][10][11] The geometry adopted for these studies was however severely limiting the sensitivity, and imposing stringent limitations for the electrochemical conditions (especially in terms of mass-transport limitations), which have direct impact on the obtained results. [ 12 ] Here, we use an alternative approach based on the multiple-internal-refl ection geometry, which allows for benefi ting from an enhanced sensitivity and working in electrochemical conditions similar to those of standard batteries for studying thin-fi lm electrodes. As shown hereafter, such a capability provides useful information of direct relevance for both interfacial and bulk electrode processes.The present study has been devoted to silicon electrodes, studied in a half-cell confi guration against a lithium-metal electrode. Silicon represents an impressive gain in energy density for negative electrodes in Li-ion batteries. One strategy to overcome the poor capacity retention associated with the massive volume expansion of silicon during lithiation is the use of nanosized geometries, for instance, particles, [13][14][15][16] wires, [17][18][19] and tubes. [ 20,21 ] The use of a thin-fi lm geometry also prevents Multiple-internal-refl ection infrared spectroscopy allows for the study of thin-fi lm amorphous silicon electrodes in situ and in operando, in conditions typical of those used in Li-ion batteries. It brings an enhanced sensitivity, and the attenuated-total-refl ection geometry allows for the extraction of quantitative information. When electrodes are cycled in representative electrolytes, the simultaneously recorded infrared spectra give an insight into the solid/electrolyte interphase (SEI) composition. They also unravel the dynamic behavior of this SEI layer by quantitatively assessing its thickness, which increases during silicon lithiation and partially decreases during delithiation. Li-ion solvation ...

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Conformations of dimethyl carbonate and its complexes with water: A matrix isolation infrared and ab initio study

Cited by 34 publications

References 30 publications

Does a hydrogen bonded complex with dual contacts show synergism? A matrix isolation infrared and ab-initio study of propargyl alcohol–water complex

Does a hydrogen bonded complex with dual contacts show synergism? A matrix isolation infrared and ab-initio study of propargyl alcohol–water complex

Role of Mixed Solvation and Ion Pairing in the Solution Structure of Lithium Ion Battery Electrolytes

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

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