Neutron diffraction and MD studies of LiBr hydrated melts

Kameda, Yasuo; Imano, Masahiro; Takeuchi, Munetaka; Suzuki, Shun; Usuki, Takeshi; Uemura, Osamu

doi:10.1016/s0022-3093(01)00757-8

Cited by 7 publications

(4 citation statements)

References 18 publications

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“…The solvation number was evaluated to be 1.86(8) and 1.86(3) in EMI + TFSI - and BMP + TFSI - , respectively, which indicates that two TFSI - ions bind to the lithium ion in both ionic liquids, if we take into account experimental errors. The result is in good agreement with the that reported by Lassègues et al It has been established that the lithium ion prefers a tetrahedrally 4-coordinated structure with O donor ligands in aqueous and nonaqueous solutions. ,, It is thus plausible that the TFSI - ion binds to the lithium ion as a bidentate O donor ligand in the ionic liquids. Indeed, according to ab initio calculations for the Li + TFSI - ion pair, the lithium ion is coordinated with two sulfonyl groups through the O atom.…”

Section: Resultssupporting

confidence: 91%

“…Lithium is used as a material for ubiquitous power sources, not only an electrolyte for secondary batteries but also a polymer or solid electrolyte. Solvation of the lithium ion has thus been investigated in aqueous solution, as well as nonaqueous solution in view of the structure and dynamics . Recently, room-temperature ionic liquids (RTILs) have been paid increasing attention as new solvents of negligible vapor pressure and incombustibility.…”

Section: Introductionmentioning

confidence: 99%

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Lithium Ion Solvation in Room-Temperature Ionic Liquids Involving Bis(trifluoromethanesulfonyl) Imide Anion Studied by Raman Spectroscopy and DFT Calculations

et al. 2007

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The solvation structure of the lithium ion in room-temperature ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl) imide (EMI(+)TFSI(-)) and N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (BMP(+0TFSI(-)) has been studied by Raman spectroscopy and DFT calculations. Raman spectra of EMI(+)TFSI(-) and BMP(+)TFSI(-) containing Li(+)TFSI(-) over the range 0.144-0.589 and 0.076-0.633 mol dm(-3), respectively, were measured at 298 K. A strong 744 cm-1 band of the free TFSI(-) ion in the bulk weakens with increasing concentration of the lithium ion, and it revealed by analyzing the intensity decrease that the two TFSI(-) ions bind to the metal ion. The lithium ion may be four-coordinated through the O atoms of two bidentate TFSI(-) ions. It has been established in our previous work that the TFSI(-) ion involves two conformers of C(1) (cis) and C(2) (trans) symmetries in equilibrium, and the dipole moment of the C(1) conformer is significantly larger than that of the C(2) conformer. On the basis of these facts, the geometries and SCF energies of possible solvate ion clusters [Li(C(1)-TFSI(-))(2)](-), [Li(C(1)-TFSI(-))(C(2)-TFSI(-))](-), and [Li(C(2)-TFSI(-))(2)](-) were examined using the theoretical DFT calculations. It is concluded that the C(1) conformer is more preferred to the C(2) conformer in the vicinity of the lithium ion.

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Section: Resultssupporting

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Lithium Ion Solvation in Room-Temperature Ionic Liquids Involving Bis(trifluoromethanesulfonyl) Imide Anion Studied by Raman Spectroscopy and DFT Calculations

et al. 2007

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“…In addition, according to a recent Raman spectroscopic study by Lassègues et al, it has been elucidated that an apparent Li + ion solvation number in the TFSA based ionic liquid decreases from 2 at a higher x Li , indicating the formation of oligomers consisting of multiple Li + ions and TFSA – anions . Moreover, structural parameters such as the Li + –O bond length and the coordination number have been accumulated for the solvated Li + ion in aqueous and nonaqueous solvent solutions except ionic liquids. − From this literature, it is considered that the 4-fold coordinated Li + ion predominantly exists as its solvation structure with the bond length ranging from 1.9 to 2.1 Å in most solvents solvating with a monodentate manner.…”

Section: Resultsmentioning

confidence: 99%

“…Theoretical approaches such as ab initio calculations , and molecular simulations , are also useful for this purpose. Apart from ionic liquid solutions, the lithium ion solvation and the ion-paired structures in aqueous and nonaqueous solutions is well investigated by means of neutron/X-ray diffraction techniques. − …”

Section: Introductionmentioning

confidence: 99%

Liquid Structure of and Li⁺ Ion Solvation in Bis(trifluoromethanesulfonyl)amide Based Ionic Liquids Composed of 1-Ethyl-3-methylimidazolium and N-Methyl-N-propylpyrrolidinium Cations

et al. 2011

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Liquid structures of the bis(trifluoromethanesulfonyl)amide based ionic liquids composed of 1-ethyl-3-methylimidazolium and N-methyl-N-propylpyrrolidinium ([C(2)mIm(+)][TFSA(-)] and [C(3)mPyrro(+)][TFSA(-)], respectively) and Li(+) ion solvation structure in their lithium salt solutions were studied by means of high-energy X-ray diffraction (HEXRD) technique with the aid of MD simulations. With regard to neat ionic liquids, a small but significant difference was found at around 3.5 Å in the intermolecular radial distribution functions G(inter)(r)s for these two ionic liquids; i.e., G(inter)(r) for [C(2)mIm(+)][TFSA(-)] was positioned at a slightly shorter region relative to that for [C(3)mPyrro(+)][TFSA(-)], which suggests that the nearest neighboring cation-anion interaction in the imidazolium ionic liquid is slightly greater than that in the other. With regard to Li(+) ion solvation structure, G(inter)(r)s for [C(2)mIm(+)][TFSA(-)] dissolving Li(+) ion exhibited additional small peak of about 1.9 Å attributable to the Li(+)-O (TFSA(-)) atom-atom correlation, though the corresponding peak was unclear in [C(3)mPyrro(+)][TFSA(-)] due to overlapping with the intramolecular atom-atom correlations in [C(3)mPyrro(+)]. In addition, the long-range density fluctuation observed in the neat ionic liquids diminished with the increase of Li(+) ion concentration for both ionic liquid solutions. These observations indicate that the large scale Li(+) ion solvated clusters are formed in the TFSA based ionic liquids, and well support the formation of [Li(TFSA)(2)](+) cluster clarified by previous Raman spectroscopic studies. MD simulations qualitatively agree with the experimental facts, by which the decrease in the long-range oscillation amplitude of r(2){G(r) - 1} for the Li(+) containing ionic liquids can be ascribed to the variation in the long-range anion-anion correlations caused by the formation of the Li(+) ion solvated clusters.

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Ab Initio Molecular Dynamics Studies of Ionic Dissolution and Precipitation of Sodium Chloride and Silver Chloride in Water Clusters, NaCl(H₂O)_n and AgCl(H₂O)_n, n = 6, 10, and 14

Siu

Fox-Beyer

Beyer

et al. 2006

Chemistry A European J

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An ab initio molecular dynamics method was used to compare the ionic dissolution of soluble sodium chloride (NaCl) in water clusters with the highly insoluble silver chloride (AgCl). The investigations focused on the solvation structures, dynamics, and energetics of the contact ion pair (CIP) and of the solvent-separated ion pair (SSIP) in NaCl(H(2)O)(n) and AgCl(H(2)O)(n) with cluster sizes of n = 6, 10 and 14. We found that the minimum cluster size required to stabilize the SSIP configuration in NaCl(H(2)O)(n) is temperature-dependent. For n = 6, both configurations are present as two distinct local minima on the free-energy profile at 100 K, whereas SSIP is unstable at 300 K. Both configurations, separated by a low barrier (<10 kJ mol(-1)), are identifiable on the free energy profiles of NaCl(H(2)O)(n) for n = 10 and 14 at 300 K, with the Na(+)/Cl(-) pairs being internally solvated in the water cluster and the SSIP configuration being slightly higher in energy (<5 kJ mol(-1)). In agreement with the low bulk solubility of AgCl, no SSIP minimum is observed on the free-energy profiles of finite AgCl(H(2)O)(n) clusters. The AgCl interaction is more covalent in nature, and is less affected by the water solvent. Unlike NaCl, AgCl is mainly solvated on the surface in finite water clusters, and ionic dissolution requires a significant reorganization of the solvent structure.

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Neutron diffraction and MD studies of LiBr hydrated melts

Cited by 7 publications

References 18 publications

Lithium Ion Solvation in Room-Temperature Ionic Liquids Involving Bis(trifluoromethanesulfonyl) Imide Anion Studied by Raman Spectroscopy and DFT Calculations

Lithium Ion Solvation in Room-Temperature Ionic Liquids Involving Bis(trifluoromethanesulfonyl) Imide Anion Studied by Raman Spectroscopy and DFT Calculations

Liquid Structure of and Li⁺ Ion Solvation in Bis(trifluoromethanesulfonyl)amide Based Ionic Liquids Composed of 1-Ethyl-3-methylimidazolium and N-Methyl-N-propylpyrrolidinium Cations

Ab Initio Molecular Dynamics Studies of Ionic Dissolution and Precipitation of Sodium Chloride and Silver Chloride in Water Clusters, NaCl(H₂O)_n and AgCl(H₂O)_n, n = 6, 10, and 14

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Neutron diffraction and MD studies of LiBr hydrated melts

Cited by 7 publications

References 18 publications

Lithium Ion Solvation in Room-Temperature Ionic Liquids Involving Bis(trifluoromethanesulfonyl) Imide Anion Studied by Raman Spectroscopy and DFT Calculations

Lithium Ion Solvation in Room-Temperature Ionic Liquids Involving Bis(trifluoromethanesulfonyl) Imide Anion Studied by Raman Spectroscopy and DFT Calculations

Liquid Structure of and Li+ Ion Solvation in Bis(trifluoromethanesulfonyl)amide Based Ionic Liquids Composed of 1-Ethyl-3-methylimidazolium and N-Methyl-N-propylpyrrolidinium Cations

Ab Initio Molecular Dynamics Studies of Ionic Dissolution and Precipitation of Sodium Chloride and Silver Chloride in Water Clusters, NaCl(H2O)n and AgCl(H2O)n, n = 6, 10, and 14

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Liquid Structure of and Li⁺ Ion Solvation in Bis(trifluoromethanesulfonyl)amide Based Ionic Liquids Composed of 1-Ethyl-3-methylimidazolium and N-Methyl-N-propylpyrrolidinium Cations

Ab Initio Molecular Dynamics Studies of Ionic Dissolution and Precipitation of Sodium Chloride and Silver Chloride in Water Clusters, NaCl(H₂O)_n and AgCl(H₂O)_n, n = 6, 10, and 14