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Register a new userAnti-electrostatic hydrogen bonding between anions of ionic liquids: A density functional theory study
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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.
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Structures and minimum molecular electrostatic potential (MEP) distributions in anacardic acid and some of its derivatives have been studied by full geometry optimization at the M06-2X/6-31G(d,p), WB97XD/6-31G(d,p) and B3LYP/6-31G(d,p) levels of density functional theory (DFT) in gas phase as well as in DMSO and aqueous solutions. Solvent effect was treated employing the integral equation formalism of the polarizable continuum model. Effects of modifications of the C1-side chain on the minimum MEP values in various regions were studied. Minimum MEP values near the oxygen atoms of the C2-OH group, oxygen or sulfur atoms of the C1-attached urea or thiourea groups and above or below the ring plane considered to be involved in interaction with the receptor were used to perform multiple linear regression. Experimentally observed anti-bacterial activities of these molecules against S. aureus are thus shown to be related to minimum MEP values in the above mentioned regions. Among the three DFT functionals used in the study, the M06-2X functional is found to yield most reliable results. Anti-bacterial activities have been predicted for certain molecules of the class which need to be verified experimentally.
Nowadays, hydrogen activation by frustrated Lewis pairs (FLPs) and their applications have been demonstrated to be one of emerge research topics in the field of catalysis. Previous studies have shown that the thermodynamics of these reaction is determined by electronic structures of FLPs and solvents. Herein, we investigated the systems consisting of typical FLPs and ionic liquids (ILs), which are well known by their large number of types and excellent solvent effects. The density functional theory (DFT) calculations were performed to study the thermodynamics for H2 activation by both inter- and intra-molecular FLPs, as well as the individual components. The results show that the computed overall Gibbs free energies in ILs are more negative than that computed in toluene. Through the thermodynamics partitioning, we find that ILs favor the H-H cleavage elemental step, while disfavored the elemental steps of proton attachment, hydride attachment and zwitterionic stabilization. Moreover, the results show that these effects are strongly dependent on the type of FLPs, where intra-molecular FLPs are more effected compared to the inter-molecular FLPs.
Standard flavors of density-functional theory (DFT) calculations are known to fail in describing anions, due to large self-interaction errors. The problem may be circumvented by using localized basis sets of reduced size, leaving no variational flexibility for the extra electron to delocalize. Alternatively, a recent approach exploiting DFT evaluations of total energies on electronic densities optimized at the Hartree-Fock (HF) level has been reported, showing that the self-interaction-free HF densities are able to lead to an improved description of the additional electron, returning affinities in close agreement with the experiments. Nonetheless, such an approach can fail when the HF densities are too inaccurate. Here, an alternative approach is presented, in which an embedding environment is used to stabilize the anion in a bound configuration. Similarly to the HF case, when computing total energies at the DFT level on these corrected densities, electron affinities in very good agreement with experiments can be recovered. The effect of the environment can be evaluated and removed by an extrapolation of the results to the limit of vanishing embedding. Moreover, the approach can be easily applied to DFT calculations with delocalized basis sets, e.g. plane-waves, for which alternative approaches are either not viable or more computationally demanding. The proposed extrapolation strategy can be thus applied also to extended systems, as often studied in condensed-matter physics and materials science, and we illustrate how the embedding environment can be exploited to determine the energy of an adsorbing anion - here a chloride ion on a metal surface - whose charge configuration would be incorrectly predicted by standard density functionals.
The treatment of atomic anions with Kohn-Sham density functional theory (DFT) has long been controversial since the highest occupied molecular orbital (HOMO) energy, $E_{HOMO}$, is often calculated to be positive with most approximate density functionals. We assess the accuracy of orbital energies and electron affinities for all three rows of elements in the periodic table (H-Ar) using a variety of theoretical approaches and customized basis sets. Among all of the theoretical methods studied here, we find that a non-empirically tuned range-separated approach (constructed to satisfy DFT-Koopmans theorem for the anionic electron system) provides the best accuracy for a variety of basis sets - even for small basis sets where most functionals typically fail. Previous approaches to solve this conundrum of positive $E_{HOMO}$ values have utilized non-self-consistent methods; however electronic properties, such as electronic couplings/gradients (which require a self-consistent potential and energy), become ill-defined with these approaches. In contrast, the non-empirically tuned range-separated procedure used here yields well-defined electronic couplings/gradients and correct $E_{HOMO}$ values since both the potential and resulting electronic energy are computed self-consistently. Orbital energies and electron affinities are further analyzed in the context of the electronic energy as a function of electronic number (including fractional numbers of electrons) to provide a stringent assessment of self-interaction errors for these complex anion systems.
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.
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