Simulation of interfaces between room temperature ionic liquids and other liquids

The structure and properties of the interfaces between the room temperature ionic liquid dimethylimidazolium chloride ([dmim]Cl) and different Lennard-Jones fluids and between ionic liquid and water have been studied by molecular dynamics simulations, and compared to the ionic liquid-vapour interface. Two contrasting types of interface were investigated, thermodynamically stable interfaces between ionic liquid and vapour and between ionic liquid and Lennard-Jones fluids, and diffusing interfaces between miscible phases of different compositions involving water. The density profiles of different species through the interface are presented. The cations and water molecules near the former type of interface are aligned relative to the surface, but no orientational preference was found near or in the broad diffusing interface. The ionic liquid has a negative electrostatic potential relative to vapour or Lennard-Jones fluid, but is more positive than pure water. This contrast is explained in terms of the relative importance of orientation and concentration differences in the two types of interface.

DFT studies of long-chain FAMEs: theoretical justification for determining chain length and unsaturation from experimental Raman spectra

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of a series of long-chain, saturated fatty acid methyl esters (FAMEs) with the formula CH2nO2 (n = 5-21) and two series of unsaturated FAMEs. The calculations showed that the lowest energy conformer within the saturated FAMEs is the simple (all-trans) structure and, in general, it was possible to reproduce experimental data using calculations on only the all-trans conformer. The only exception was C6H12O2, where a second low-lying conformer had to be included in order to correctly simulate the experimental Raman spectrum. The objective of the work was to provide theoretical justification for the methods that are commonly used to determine the properties of the fats and oils, such as chain length and degree of unsaturation, from experimental Raman data. Here it is shown that the calculations reproduce the trends and calibration curves that are found experimentally and also allow the reasons for the failure of what would appear to be rational measurements to be understood. This work shows that although the assumption that each FAME can simply be treated as a collection of functional groups can be justified in some cases, many of the vibrational modes are complex motions of large sections of the molecules and thus would not be expected to show simple linear trends with changes in structure, such as increasing chain length and/or unsaturation. Simple linear trends obtained from experimental data may thus arise from cancellation of opposing effects, rather than reflecting an underlying simplicity.

Conformations, vibrational frequencies and Raman intensities of short-chain fatty acid methyl esters using DFT with 6-31G(d) and Sadlej pVTZ basis sets

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of three short-chain fatty acid methyl esters (FAMEs) with the formula CnH2nO2 (n = 3-5). In all three FAMEs, the lowest energy conformer has a simple 'all-trans' structure but there are other conformers, with different torsions about the backbone, which lie reasonably close in energy to the global minimum. One result of this is that the solid samples we studied do not appear to consist entirely of the lowest energy conformer. Indeed, to account for the 'extra' bands that were observed in the Raman data but were not predicted for the all-trans conformer, it was necessary to add-in contributions from other conformers before a complete set of vibrational assignments could be made. Provided this was done, the agreement between experimental Raman frequencies and 6-31G(d) values (after scaling) was excellent, RSD = 12.6 cm(-1). However, the agreement between predicted and observed intensities was much less satisfactory. To confirm the validity of the approach followed by the 6-3 1 G(d) basis set, we used a larger basis set, Sadlej pVTZ, and found that these calculations gave accurate Raman intensities and simulated spectra (summed from two different conformers) that were in quantitative agreement with experiment. In addition, the unscaled Sadlej pVTZ, and the scaled 6-3 1 G(d) calculations gave the same vibrational mode assignments for all bands in the experimental data. This work provides the foundation for calculations on longer-chain FAMEs (which are closer to those found as triglycerides in edible fats and oils) because it shows that scaled 6-3 1 G(d) calculations give equally accurate frequency predictions, and the same vibrational mode assignments, as the much more CPU-expensive Sadlej pVTZ basis set calculations.

Understanding the dehydrogenation mechanism of tetrahydrocarbazole over palladium using a combined experimental and density functional theory approach

The mechanism of the dehydrogenation of tetrahydrocarbazole to carbazole over palladium has been examined for the first time. By use of a combination of deuterium exchange experiments and density functional theory calculations, a detailed reaction profile for the aromatization of tetrahydrocarbazole has been identified and validated by experiment. As with many dehydrogenation reactions, the initial hydrogen abstraction is found to have the highest reaction barrier. Tetrahydrocarbazole has four hydrogens which can, in principle, be cleaved initially; however, the theory and experiment show that the reaction is dominated by the cleavage of the carbon hydrogens at the carbon atoms in positions 1 and 4. The two pathways originating from these two C-H bond cleavage processes are found to have similar reaction energy profiles and both contribute to the overall reaction.

Resonance Raman and lifetime studies on regioselectively deuteriated ruthenium (II) polypyridyl complexes

Two series of ruthenium(II) polypyridyl complexes [Ru(bipy)2(phpytr)]+ and [Ru(bipy)2(phpztr)]+ (where Hphpytr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyridine and Hphpztr = 2-(5-phenyl-1H-[1,2,4]triazol-3-yl)-pyrazine) are examined by electrochemistry, UV/Vis, emission, resonance Raman, transient resonance Raman and transient absorption spectroscopy, in order to obtain a more comprehensive understanding of their excited state electronic properties. The interpretation of the results obtained is facilitated by the availability of several isotopologues of each of the complexes examined. For the pyridine-1,2,4-triazolato based complex the lowest emissive excited state is exclusively bipy based, however, for the pyrazine based complexes excited state localisation on particular ligands shows considerable solvent and pH dependency.

Raman and ab initio studies of simple and binary 1-Alkyl-3-methylimidazolium ionic liquids

Raman spectra of the ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF(6)]), 1-hexyl-3-methylimidazolium chloride ([C(6)mim]Cl), and 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)mim][PF(6)]), and binary mixtures thereof, have been assigned using ab initio MP2 calculations. The previously reported anti and gauche forms of the [C(4)mim](+) cation have been observed, and this study reveals this to be a general feature of the long-chain I-alkyl derivatives. Analysis of mixtures Of [C(6)mim]Cl and [C(6)mim][PF(6)] has provided information on the nature of the hydrogen bonding between the imidazolium headgroup and the anions, and the invariance of the essentially 50:50 mixture of the predominant conformers informs on the nature of glass formation in these systems.

On the origin of the forward peak and backward oscillations in the F + H2(v = 0) to HF(v' = 2) + H reaction

We present a semiclassical complex angular momentum (CAM) analysis of the forward scattering peak which occurs at a translational collision energy around 32 meV in the quantum mechanical calculations for the F + H2(v = 0, j = 0) ? HF(v' = 2, j' = 0) + H reaction on the Stark–Werner potential energy surface. The semiclassical CAM theory is modified to cover the forward and backward scattering angles. The peak is shown to result from constructive/destructive interference of the two Regge states associated with two resonances, one in the transition state region and the other in the exit channel van der Waals well. In addition, we demonstrate that the oscillations in the energy dependence of the backward differential cross section are caused by the interference between the direct backward scattering and the decay of the two resonance complexes returning to the backward direction after one full rotation.

Viscosity of binary mixtures of cycloalkane with cycloalkane, alkane and aromatic hydrocarbon at 303.15 K

The viscosity ? for eighteen binary mixtures cyclopentane + cyclohexane and + cyclooctane; cyclohexane + cycloheptane, + cyclooctane, + methylcyclohexane, + n-hexane, + n-heptane, + n-octane, + i-octane, + benzene, + toluene, + ethylbenzene, + p-xylene, and + propylbenzene; methylcyclohexane + n-hexane, + i-octane, and + benzene; and cyclooctane + benzene have been reported at 303.15 K over the entire range of composition. The viscosity deviations ?? and excess Gibbs energy of activation ?G*E of viscous flow based on Eyring's theory have been calculated. The effects of molecular sizes and shapes of the component molecules and of interaction energy in the mixture have been discussed. The viscosity data have been correlated with the equations of Grunberg and Nissan, Hind, McLaughlin and Ubbelohde, Tamura and Kurata, Katti and Chaudhri, McAllister, Heric and Brewer, and of Auslaender.

Speeds of sound and isentropic compressibilities of binary mixtures containing trialkylamines with alkanes and mono-alkylamines at 303.15 and 313.15 K

Isentropic compressibilities ?S, and excess isentropic compressibilities ?SE have been determined from measurements of speeds of sound u and densities ? of 14 binary mixtures of triethylamine (TEA) and tri-n-butylamine (TBA) with n-hexane, n-octane, iso-octane, n-propylamine, n-butylamine, n-hexylamine and n-octylamine. The relative magnitude and sign of ?SE have been interpreted in terms of molecular interactions and interstitial accommodation. The values of ?SE for TEA + alkane are positive while for TBA + alkane are negative. The values of ?SE for TEA + primary amine become progressively less positive and eventually to negative with the increase in chain length of alkylamine. In case of TBA + primary amine, the values of ?SE increase from n-propylamine to n-butylamine, and then decrease with chain length of primary amine. The experimental speeds of sound u have been analyzed in terms of collision factor theory, free length theory and Prigogine–Flory–Patterson statistical theory of solutions.

Acoustic, volumetric, compressibility and refractivity properties and Flory’s reduction parameters of some homologous series of alkyl alkanoates from 298.15 to 333.15 K

The speeds of sound u in, densities ? and refractive indices nD of some homologous series, such as n-alkyl ethanoates, n-alkyl propionates, methyl alkanoates, ethyl alkanoates, dialkyl malonates, and alkyl haloalkanoates, were measured in the temperature range from 298.15 to 333.15 K. Molar volume V, isentropic and isothermal compressibilities ?S and ?T, molar refraction Rm, Eykman’s constant Cm, molecular radius r, Rao’s molar function R, thermal expansion coefficient a, thermal pressure coefficient ?, and Flory’s characteristic parameters image, P*, V*, and T* have been calculated from the measured experimental data. Applicability of Rao theory and Flory–Patterson–Pandey (FPP) theory have been examined and discussed for these alkanoates.

Speeds of sound, isentropic compressibilities, and excess molar volumes of cycloalkanes, alkanes and aromatic hydrocarbons at 303.15 K. II. Results for cycloalkanes+aromatic hydrocarbons

The speeds of sound u, isentropic compressibilities ?S, molar sound functions R, excess isentropic compressibilities ?SE and excess molar volumes VE for eight binary mixtures of cyclopentane, cyclohexane, cyclooctane and methylcyclohexane with benzene and of cyclohexane with toluene, ethyl benzene, p-xylene and propyl benzene at 303.15 K are reported. The effects of molecular sizes and shapes of the component molecules and of interaction energy in the mixture have been discussed. The Prigogine–Flory–Patterson theory has been applied to analyze the present binary mixtures along with the mixtures of cis- and trans-decalins with benzene and toluene taken from the literature.

Acoustic, volumetric, compressibility and refractivity properties and reduction parameters for the ERAS and Flory models of some homologous series of amines from 298.15 to 328.15 K

The speeds of sound u, densities ? and refractive indices nD of homologous series of mono-, di-, and tri-alkylamines were measured in the temperature range from 298.15 to 328.15 K. Isentropic and isothermal compressibilities ?S and ?T, molar refraction Rm, Eykman’s constant Cm, Rao’s molar sound function R, thermal expansion coefficient a, thermal pressure coefficient ?, and reduction parameters P*, V*, and T* in frameworks of the ERAS model for associated amines and Flory model for tertiary amines have been calculated from the measured experimental data. Applicability of the Rao theory and the ERAS and Flory models have been examined and discussed for the alkyl amines.

Densities, speeds of sound, isentropic compressibilities, refractive indices and viscosities of binary mixtures of tetrahydrofuran with hydrocarbons at 303.15 K

Isentropic compressibilities, Rao's molar sound functions, molar refractions, excess isentropic compressibilities, excess molar volumes, viscosity deviations and excess Gibbs energies of activation of viscous flow for seven binary mixtures of tetrahydrofuran (THF) with cyclohexane, methylcyclohexane, n-hexane, benzene, toluene, p-xylene and propylbenzene over the entire range of composition at 303.15 K have been derived from experimental densities, speeds of sound, refractive indices and viscosities. The excess partial molar volumes of THF in different solvents have been estimated. The experimental results have been analyzed in terms of the Prigogine–Flory–Patterson theory.

Densities, speeds of sound, isentropic compressibilities, refractive indexes, and viscosities of tetrahydrofuran with haloalkane or alkyl ethanoate at T = 303.15 K

Isentropic compressibilities ?S, excess isentropic compressibilities image, excess molar volumes VE, viscosity deviations ??, and excess Gibbs energy of activation of viscous flow ?G*E for nine binary mixtures of C4H8O with CCl4, CHCl3, CHCl2CHCl2, 1-C6H13Cl, 1-C6H13Br, CH3CO2CH3, CH3CO2C2H5, CH3CO2C4H9, and CH3CO2C5H11 at 303.15 K have been derived from experimental densities ?, speeds of sound u, refractive indexes nD and viscosities ?. The limiting values of excess partial molar volumes of C4H8O at infinite dilution image in different solvents have been estimated. The results obtained for dynamic viscosity of binary mixtures were used to test the semi-empirical relations of Grunberg–Nissan, Tamura–Kurata, Hind–McLaughlin–Ubbelohde, Katti–Chaudhri, McAllister, Heric, and Auslaender. Finally, the experimental refractive indexes were compared with the predicted results for Lorentz–Lorenz, Dale–Gladstone, Eykman, Arago–Boit, Newton, Oster, Heller, and Wiener equations.