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Register a new userHow Molecular Chiralities of Bis(mandelato)borate Anions affect Their Binding Structures with Alkali Metal Ions and Microstructural Properties in Tetraalkylphosphonium Ionic Liquids
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Spiroborate anions based inorganic electrolytes and ionic liquids (ILs) have fascinating electrochemical and tribological properties, and have received widespread attention in industrial applications. Molecular chiralities of spiroborate anions have a significant effect on microstructures and macroscopic functionalities of these ionic materials in applications, and thus deserve a fundamental understanding. In current work, we performed quantum chemistry calculations to address binding strength and coordination structures of chiral bis(mandelato)borate ([BMB]) anions with representative alkali metal ions, as well as electronic properties of alkali metal ion-[BMB] ion pair complexes. The optimized [BMB] conformers are categorized into V-shaped, bent, and twisted structures with varied electrostatic potential contours, conformational energies, and distinct alkali metal ion-[BMB] binding structures. Alkali metal ions have additional associations with phenyl groups in V-shaped [BMB] conformers owing to preferential cation-$pi$ interactions. Furthermore, effects of molecular chiralities of [BMB] anions on thermodynamics and microstructural properties of tetraalkylphosphonium [BMB] ILs were studied by performing extensive atomistic interactions. Oxygen atoms in [BMB] anions have competitive hydrogen bonding interactions with hydrogen atoms in cations depending on molecular chiralities and steric hindrance effects of [BMB] anions. However, molecular chiralities of [BMB] anions have negligible effect on liquid densities of tetraalkylphosphonium [BMB] ILs and spatial distributions of boron atoms in anions around phosphorous atoms in cations. Enlarging tetraalkylphosphonium cation sizes leads to enhanced cation-anion hydrogen bonding and Coulombic interactions due to enhanced segregation of polar groups in apolar networks in heterogeneous IL matrices.
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Room Temperature Ionic Liquids (RTILs) have attracted much of the attention of the scientific community in the past decade due the their novel and highly customizable properties. Nonetheless their high viscosities pose serious limitations to the use of RTILs in practical applications. To elucidate some of the physical aspects behind transport properties of RTILs, extensive classical molecular dynamics (MD) calculations are reported. Bulk viscosities and ionic conductivities of butyl-methyl-imidazole based RTILs are presented over a wide range of temperatures. The dependence of the properties of the liquids on simulation parameters, e.g. system size effects and choice of the interaction potential, is analyzed.
Hydrogen bonds (HBs) play a crucial role in the physicochemical properties of ionic liquids (ILs). At present, HBs between cations and anions (Ca-An) or between cations (Ca-Ca) in ILs have been reported extensively. Here, we provided DFT evidences for the exists of HBs between anions (An-An) in the IL 1-(2-hydroxyethyl)-3-methylimidazolium 4-(2-hydroxyethyl)imidazolide [HEMIm][HEIm]. The thermodynamics stabilities of anionic, cationic, and H2O dimers together with ionic pairs were studied by potential energy scans. The results show that the cation-anion pair is the most stable one, while the HB in anionic dimer possesses similar thermodynamics stability to the water dimer. The further geometric, spectral and electronic structure analyses demonstrate that the inter-anionic HB meets the general theoretical criteria of traditional HBs. The strength order of four HBs in complexes is cation-anion pair > H2O dimer = cationic dimer > anionic dimer. The energy decomposition analysis indicates that induction and dispersion interactions are the crucial factors to overcome strong Coulomb repulsions, forming inter-anionic HBs. Lastly, the presence of inter-anionic HBs in ionic cluster has been confirmed by a global minimum search for a system containing two ionic pairs. Even though hydroxyl-functionalized cations are more likely to form HBs with anions, there still have inter-anionic HBs between hydroxyl groups in the low-lying structures. Our studies broaden the understanding of HBs in ionic liquids and support the recently proposed concept of anti-electrostatic HBs.
Steric hindered frustrated Lewis pairs (FLPs) have been shown to activate hydrogen molecules, and their reactivity is strongly determined by the geometric parameters of the Lewis acid s and bases. A recent experimental study showed that ionic liquids (ILs) could largely improve the effective configuration of FLPs. However, the detailed mechanistic profile is still unclear. Herein, we performed a molecular dynamics (MD) simulations, aimi ng to reveal the effects of ILs on the structures of FLPs, and to present a rule for selecting more efficient reaction media. For this purpose, mixture systems were adopt consisting of the ILs [Cnmim][NTf2] (n= 6, 10, 14), and the typical FLP (tBu)3P/B(C6F5)3 . Radial distribution function (RDF) results show that toluene competes with (tBu)3P to interact with B(C6F5)3 , resulting in a relatively low effective (tBu)3P/B(C6F5)3 complex. [Cnmim][NTf2] is more intended to form a solvated shell surrounding the (tBu)3P/B(C6F5)3 , which increases the amount of effective FLPs. Spatial distribution function (SDF) results show that toluene formed a continuum solvation shell, which hinders the interactions of (tBu)3P and B(C6F5)3 , while [Cnmim][NTf2] leave a relatively large empty space, which is accessible by (tBu3)P molecules, resulting in a higher probability of Lewis acids and bases interactions. Lastly, we find that the longer alkyl chain length of[Cnmim] cations, the higher probability of effective FLPs.
Ionic transports in nanopores hold the key to unlocking the full potential of bi-continuous nanoporous (NP) metals as advanced electrodes in electrochemical devices. The precise control of the uniform NP metal structures also provides us a unique opportunity to understand how complex structures determine transports at nanoscales. For NP Au from the dealloying of a Ag-Au alloy, we can tune the pore size in the range of 13 nm to 2.4 microns and the porosity between 38% and 69% via isothermal coarsening. For NP Ag from the reduction-induced decomposition of AgCl, we can control additionally its structural hierarchy and pore orientation. We measure the effective ionic conductivities of 1 M NaClO4 through these NP metals as membranes, which range from 7% to 44% of that of a free solution, corresponding to calculated pore tortuosities between 2.7 and 1.3. The tortuosity of NP Au displays weak dependences on both the pore size and the porosity, consistent with the observed self-similarity in the coarsening, except for those of pores < 25 nm, which we consider deviating from the well-coarsened pore geometry. For NP Ag, the low tortuosity of the hierarchical structure can be explained with the Maxwell-Garnett equation and that of the oriented structure underlines the random orientation as the cause of slow transport in other NP metals. At last, we achieve high current densities of CO2 reduction with these two low-tortuosity NP Ags, demonstrating the significance of the structure-transport relationships for designing functional NP metals.
A first principles study of the dynamics of $^6$Li($^{2}$S) + $^6$Li$^{174}$Yb($^2Sigma^+$)$ to ^6$Li$_2(^1Sigma^+$) + $^{174}$Yb($^1$S) reaction is presented at cold and ultracold temperatures. The computations involve determination and analytic fitting of a three-dimensional potential energy surface for the Li$_2$Yb system and quantum dynamics calculations of varying complexities, ranging from exact quantum dynamics within the close-coupling scheme, to statistical quantum treatment, and universal models. It is demonstrated that the two simplified methods yield zero-temperature limiting reaction rate coefficients in reasonable agreement with the full close-coupling calculations. The effect of the three-body term in the interaction potential is explored by comparing quantum dynamics results from a pairwise potential that neglects the three-body term to that derived from the full interaction potential. Inclusion of the three-body term in the close-coupling calculations was found to reduce the limiting rate coefficients by a factor of two. The reaction exoergicity populates vibrational levels as high as $v=19$ of the $^6$Li$_2$ molecule in the limit of zero collision energy. Product vibrational distributions from the close-coupling calculations reveal sensitivity to inclusion of three-body forces in the interaction potential. Overall, the results indicate that a simplified model based on the long-range potential is able to yield reliable values of the total reaction rate coefficient in the ultracold limit but a more rigorous approach based on statistical quantum or quantum close-coupling methods is desirable when product rovibrational distribution is required.
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