Oleg N. Kalugin

Acetonitrile Boosts Conductivity of Imidazolium Ionic Liquids

We apply a new methodology in the force field generation (Phys. Chem. Chem. Phys.2011, 13, 7910) to study binary mixtures of five imidazolium-based room-temperature ionic liquids (RTILs) with acetonitrile (ACN). Each RTIL is composed of tetrafluoroborate (BF(4)) anion and dialkylimidazolium (MMIM) cations. The first alkyl group of MIM is methyl, and the other group is ethyl (EMIM), butyl (BMIM), hexyl (HMIM), octyl (OMIM), and decyl (DMIM). Upon addition of ACN, the ionic conductivity of RTILs increases by more than 50 times. It significantly exceeds an impact of most known solvents. Unexpectedly, long-tailed imidazolium cations demonstrate the sharpest conductivity boost. This finding motivates us to revisit an application of RTIL/ACN binary systems as advanced electrolyte solutions. The conductivity correlates with a composition of ion aggregates simplifying its predictability. Addition of ACN exponentially increases diffusion and decreases viscosity of the RTIL/ACN mixtures. Large amounts of ACN stabilize ion pairs, although they ruin greater ion aggregates.

Uniform diffusion of acetonitrile inside carbon nanotubes favors supercapacitor performance.

An unusual behavior of liquid acetonitrile (AN) confined inside carbon nanotubes (CNTs) is predicted by molecular dynamics simulation. In contrast to water, which shows inhomogeneous variation of both translational and rotational diffusion with CNT diameter [ Nano Lett. 2003, 3, 589; 2004, 4, 619], the diffusion coefficient of AN changes uniformly and can be described by a simple analytic model. At the same time, the reorientation dynamics of AN vary irregularly in smaller CNTs because of specific packing structures. The uniform translational diffusion of the nonaqueous solvent is critical for stable performance of the new generation of supercapacitors [ Nat. Mater. 2006, 5, 987].

Ab Initio Study of Phonon-Induced Dephasing of Electronic Excitations in Narrow Graphene Nanoribbons

Vibrational dephasing of the lowest energy electronic excitations in the perfect (16,16) graphene nanoribbon (GNR) and those with the C2-bond insertion and rotation defects is studied with ab initio molecular dynamics. Compared to single-walled carbon nanotubes (SWCNTs) of similar size, GNRs shows very different properties. The dephasing in the ideal GNR occurs twice faster than that in the SWCNTs. It is induced primarily by the 1300 cm (-1) disorder mode seen in bulk graphite rather than by the 1600 cm (-1) C-C stretching mode as in SWCNTs. In contrast to SWCNTs, defects exhibit weaker electron-phonon coupling compared to the ideal system. Therefore, defects should present much less of a practical problem in GNRs compared to SWCNTs. The predicted optical line widths can be tested experimentally.

Translational Diffusion in Mixtures of Imidazolium ILs with Polar Aprotic Molecular Solvents

Self-diffusion coefficients of cations and solvent molecules were determined with (1)H NMR in mixtures of 1-n-butyl-3-methylimidazolium (Bmim(+)) tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)), trifluoromethanesulfonate (TfO(-)), and bis(trifluoromethylsulfonyl)imide (TFSI(-)) with acetonitrile (AN), γ-butyrolactone (γ-BL), and propylene carbonate (PC) over the entire composition range at 300 K. The relative diffusivities of solvent molecules to cations as a function of concentration were found to depend on the solvent but not on the anion (i.e., IL). In all cases the values exhibit a plateau at low IL content (x(IL) < 0.2) and then increase steeply (AN), moderately (γ-BL), or negligibly (PC) at higher IL concentrations. This behavior was related to the different solvation patterns in the employed solvents. In BmimPF6-based systems, anionic diffusivities were followed via (31)P nuclei and found to be higher than the corresponding cation values in IL-poor systems and lower in the IL-rich region. The inversion point of relative ionic diffusivities was found around equimolar composition and does not depend on the solvent. At this point, a distinct change in the ion-diffusion mechanism appears to take place.

Microscopic structure of liquid dimethyl sulphoxide and its electrolyte solutions: molecular dynamics simulations

Molecular dynamics (MD) simulations of pure dimethyl sulphoxide (DMSO) and solutions of Na+, Ca2+, Cl−, NaCl and CaCl2 in DMSO have been performed at 298.15 K and 398.15 K in NVT ensembles by using a four-interaction-site model of DMSO and reaction field method for Coulombic interactions. The structure of solvent, ion-solvation shells and ion-pairs have been analysed by employing a concept of coordination centres and characteristic vectors of the solvent molecule. Results are given for atom-atom (corresponding to DMSO), ion-atom and ion-ion radial distribution functions (RDFs), orientation of the DMSO molecules and their geometrical arrangements in the first solvation shells of the ions (Na+, Ca2+, Cl−). A preferential formation of cyclic dimers with antiparallel alignment between dipole moments of nearest-neighbour molecules in the pure solvent is found. Geometrical models of the first coordination shells of the ions in ‘infinitely dilute solutions’ are proposed. Ion-ion RDFs in NaCl-DMSO and CaCl2-DMSO solutions reveal the presence of both solvent separated (SSIP) and contact (CIP) ion pairs. The structures of the solvation shells of such ion pairs are also discussed.

Solvation of solvophilic and solvophobic ions in dimethyl sulfoxide: microscopic structure by molecular dynamics simulations

Molecular dynamics (MD) simulations of dimethyl sulfoxide (DMSO) solutions of Li+, Me4N+, BPh4−, big spherical ions of the same size but different charge, such as S+, S−, S0 have been performed at 298 K in NVT ensembles by using a four-interacting-sites model of DMSO and reaction field method for Coulombic interactions. Similar simulations were also performed on neat DMSO in which one DMSO molecule acted as a solute. The microscopic structures of ion-solvation shells have been analysed by employing a concept of co-ordination centres and characteristic vectors of the solvent molecule. Results are given for the atom–atom and ion–atom radial distribution functions (RDFs), orientation of the DMSO molecules and their geometrical arrangements in the first solvation shells of the ions. For the solvophilic Li+, a highly symmetric and well-pronounced first solvation shell (FSS) with fixed co-ordination number is observed. The co-ordination number and geometry of the FSS of lithium ion is strongly defined by the short-range non-Coulombic interactions between the ion and the surrounding DMSO molecules. The results show the importance of charge distribution in the solvent molecule and consequently the sign of ionic charge in creating local order around the solvated ion. It is found that the DMSO solvates S+ better than S−, which is better solvated than S0. The ‘solvophobic’ nature of the big multiatomic ions in non-aqueous media creates the possibility of the solvent molecules penetrating into the solute that is typically observed from our simulations not only for the charged species like Me4N+ and BPh4−, but also for the neutral solute represented by the DMSO molecule in neat DMSO.

Control of Carbon Nanotube Electronic Properties by Lithium Cation Intercalation.

We show that the electronic properties of single walled carbon nanotubes (SWCNTs) can be tuned continuously from semiconducting to metallic by varying the location of ions inside the tubes. Focusing on the Li(+) cation inside the (26,0) zigzag semiconducting and (15,15) armchair metallic SWCNTs, we found that the Li(+)-SWCNT interaction is attractive. The interaction is stronger for the metallic SWCNT, indicating in particular that metallic tubes can enhance performance of lithium-ion batteries. The electronic properties of the metallic SWCNT are virtually independent of the presence of ions: Li(+) creates an energy level in the valence band slightly below the Fermi energy. On the contrary, the semiconducting SWCNT can be made metallic by placing ions close to the tube axis: Li(+) generates a new bottom of the conduction band. Letting the ions approach SWCNT walls recovers the semiconducting behavior.

Vibrational Energy Transfer between Carbon Nanotubes and Liquid Water: A Molecular Dynamics Study

The rates and magnitudes of vibrational energy transfer between single-wall carbon nanotubes (CNTs) and water are investigated by classical molecular dynamics. The interactions between the CNT and solvent confined inside of the tube, the CNT and solvent surrounding the tube, as well as the solvent inside and outside of the tube are considered for the (11,11), (15,15), and (19,19) armchair CNTs. The vibrational energy transfer exhibits two time scales, subpicosecond and picosecond, of roughly equal importance. Solvent molecules confined within CNTs are more strongly coupled to the tubes than the outside molecules. The energy exchange is facilitated by slow collective motions, including CNT radial breathing modes (RBM). The transfer rate between CNTs and the inside solvent shows strong dependence on the CNT diameter. In smaller tubes, the transfer is faster and the solvent coupling to RBMs is stronger. The magnitude of the CNT-outside solvent interaction scales with the CNT surface area, while that of the CNT-inside solvent exhibits scaling that is intermediate between the CNT volume and surface. The Coulomb interaction between the solvent molecules inside and outside of the CNTs is much weaker than the CNT-solvent interactions. The results indicate that the excitation energy supplied to CNTs in chemical and biological applications is rapidly deposited to the active molecular agents and should remain localized sufficiently long in order to perform the desired function.

Copper(II) complexes of 3- and 4-picolinehydroxamic acids: from mononuclear compounds to 1D- and 2D-coordination polymers

A series of copper(II) complexes with 3- and 4-picolinehydroxamic acids has been synthesized and characterized by a variety of spectroscopic methods, X-ray structure analysis and magnetic susceptibility measurements. The ligands show the tendency to form 1D- and 2D-polymeric structures with copper(II) ions due to the chelating-and-bridging binding mode involving the (O,O′)-hydroxamate chelate formation combined with N-coordination of the pyridine moiety. In some cases the (O, μ2-O′) chelating-and-bridging modes are realized, in which either amide or hydroxamic oxygen atoms play a μ2-bridging role. Molecular and crystal structures of two discrete complexes: mononuclear [Cu(3-HPicHA)2(ClO4)2] (1) and binuclear [{Cu(4-HPicHA)(bpy)(ClO4)}2](ClO4)2 (4a), and five coordination polymers catena-[Cu(3-PicHA)(phen)]n(ClO4)n (7), catena-[Cu(4-PicHA)(bpy)]n(OH)n·3.25nH2O (8), catena-[Cu(4-PicHA)(DMSO)2]2n(ClO4)2n (9), [Cu(3-PicHA)(DMSO)(ClO4)]nm·nmDMSO (10), and [{Cu(4-PicHA)(phen)}2]n(ClO4)2n (11) were determined by single crystal X-ray analysis. In structures 1 and 4a the hydroxamate ligands exist in a zwitterionic form with the O-deprotonated hydroxamate groups and protonated pyridine rings. The following types of coordination polymers have been structurally characterized: (i) single-stranded zigzag-shaped 1D polymers (7 and 8); (ii) double-stranded 1D polymer comprising binuclear subunits formed on account of μ2(O)-carbonyl oxygen bridging coordination to the axial position of the copper(II) ion (9); (iii) 2D netted coordination polymers of two different types comprising μ2(O)-bridged binuclear subunits (10 and 11). Magnetic susceptibility measurements (2–300 K) of powdered samples revealed the presence of moderate antiferromagnetic interaction in the binuclear complex 4a (2J = −7.164(6) cm−1), while the coordination polymers exhibit weak antiferromagnetic interaction with a cryomagnetic behaviour obeying the Curie–Weiss law.

Local Structure in Terms of Nearest-Neighbor Approach in 1-Butyl-3-methylimidazolium-Based Ionic Liquids: MD Simulations.

Description of the local microscopic structure in ionic liquids (ILs) is a prerequisite to obtain a comprehensive understanding of the influence of the nature of ions on the properties of ILs. The local structure is mainly determined by the spatial arrangement of the nearest neighboring ions. Therefore, the main interaction patterns in ILs, such as cation-anion H-bond-like motifs, cation-cation alkyl tail aggregation, and ring stacking, were considered within the framework of the nearest-neighbor approach with respect to each particular interaction site. We employed classical molecular dynamics (MD) simulations to study in detail the spatial, radial, and orientational relative distribution of ions in a set of imidazolium-based ILs, in which the 1-butyl-3-methylimidazolium (C4mim(+)) cation is coupled with the acetate (OAc(-)), chloride (Cl(-)), tetrafluoroborate (BF4(-)), hexafluorophosphate (PF6(-)), trifluoromethanesulfonate (TfO(-)), or bis(trifluoromethanesulfonyl)amide (TFSA(-)) anion. It was established that several structural properties are strongly anion-specific, while some can be treated as universally applicable to ILs, regardless of the nature of the anion. Namely, strongly basic anions, such as OAc(-) and Cl(-), prefer to be located in the imidazolium ring plane next to the C-H(2/4-5) sites. By contrast, the other four bulky and weakly coordinating anions tend to occupy positions above/below the plane. Similarly, the H-bond-like interactions involving the H(2) site are found to be particularly enhanced in comparison with the ones at H(4-5) in the case of asymmetric and/or more basic anions (C4mimOAc, C4mimCl, C4mimTfO, and C4mimTFSA), in accordance with recent spectroscopic and theoretical findings. Other IL-specific details related to the multiple H-bond-like binding and cation stacking issues are also discussed in this paper. The secondary H-bonding of anions with the alkyl hydrogen atoms of cations as well as the cation-cation alkyl chain aggregation turned out to be poorly sensitive to the nature of the anion.