Recasting the wobbling-in-a-cone model for the rotational anisotropy of phenylselenocyanate in poly(methyl methacrylate): Effect of internal bond rotation and polymer segmental motion.

The rotational anisotropy of a molecule in a constrained environment is modeled by wobbling-in-a-cone (WIAC) motion, which describes the angular space sampled by the molecule. Recent polarization-selective IR pump-probe measurements have applied this model to phenylselenocyanate in amorphous polymers, aiming to probe the surrounding free volume. A faster rotational timescale was hypothesized to reflect the angular space within the static voids of the polymer matrix, while a slower timescale relates to constraint release by the polymer backbones.

Do Electrostatics Control the Diffusive Dynamics of Solitary Water? NMR and MD Studies of Water Translation and Rotation in Dipolar and Ionic Solvents.

NMR-based measurements of the diffusion coefficients and rotation times of solitary water and benzene at 300 K are reported in a diverse collection of 13 conventional organic solvents and 10 imidazolium ionic liquids. Proton chemical shifts of water are found to be correlated to water OH-stretching frequencies, confirming the importance of electrostatic interactions in these shifts. However, the influence of magnetic interactions in aromatic solvents renders chemical shifts a less reliable indicator of electrostatics.

What do far-infrared spectra of solitary water in "water-in-solvent" systems reveal about water's solvation and dynamics?

Classical molecular dynamics simulations of water in ionic and dipolar solvents were used to interpret the far-infrared (FIR) rotation/libration spectra of "solitary water" in terms of water's rotational dynamics and interactions with solvents. Seven solvents represented by nonpolarizable all-atom force fields and a series of idealized variable-charge solvents were used to span the range of solvent polarities (hydrogen bonding) studied experimentally. Simulated spectra capture the solvent dependence observed, as well as the relationship between the frequencies of water libration (νL) and OH stretching bands (νOH).

Rapid water dynamics structures the OH-stretching spectra of solitary water in ionic liquids and dipolar solvents.

In a recent study [J. Phys. Chem.

OH Stretching and Libration Bands of Solitary Water in Ionic Liquids and Dipolar Solvents Share a Single Dependence on Solvent Polarity.

Ionic liquids are an emerging class of materials which are finding application in a variety of technologically important areas. Because of their hydrophilic character, at least a small concentration of water is often present when ionic liquids are used in practical applications. This study employs infrared spectroscopy in the OH stretching and libration regions together with DFT calculations to better characterize the state of dilute water in ionic liquids.

Unraveling the Sorption Mechanism of CO in a Molecular Crystal without Intrinsic Porosity.

The facile uptake of CO gas in a nonporous molecular crystal constituted by long molecules with carbazole and ethynylphenyl moieties was reported in experiments recently. Herein, the mechanism of gas uptake by this crystal is elucidated using atomistic molecular simulations. The uptake of CO is shown to be facilitated by (i) the capacity of the crystal to expand in volume because of weak intermolecular interactions, (ii) the parallel orientation of the long molecules in the crystal, and (iii) the ability of the molecule to marginally bend, yet not lose crystallinity because of the anchoring of the terminal carbazole groups.

Solvation of Methyl Lactate in Water: Molecular Dynamics Studies.

Methyl lactate (ML), a chiral α-hydroxy ester, has been probed widely to understand the competition between two types of intramolecular H-bonds in solvents of different polarities. Recent experimental and high-level quantum chemical studies have revealed the predominant existence of ML-water insertion complexes over addition complexes in aqueous solution. Although the stability of monohydrate insertion conformer was studied accurately, ab initio quantum chemical calculations failed to predict the most stable dihydrate conformer in analogy with the experimental spectroscopic search.

Self-Assembly of Cations in Aqueous Solutions of Hydroxyl-Functionalized Ionic Liquids: Molecular Dynamics Studies.

The effect of presence of a hydroxyl-functionalized alkyl chain of varying carbon number on the self-assembly of cations in aqueous solutions of 1-(n-hydroxyalkyl)-3-decylimidazolium bromide (where the alkyl groups are ethyl, butyl, heptyl, and decyl) has been studied using atomistic molecular dynamics simulations. Spontaneous self-assembly of cations to form aggregates with hydrophobic core and hydrophilic surface is observed. The shape of the aggregates changes from quasispherical in the case of cations with hydroxyheptyl or smaller substituent chain, to a thin film like intercalated aggregate in the case of cations with hydroxydecyl chain.

Segregation of ions at the interface: molecular dynamics studies of the bulk and liquid-vapor interface structure of equimolar binary mixtures of ionic liquids.

The structures of three different equimolar binary ionic liquid mixtures and their liquid-vapor interface have been studied using atomistic molecular dynamics simulations. Two of these binary mixtures were composed of a common cation 1-n-butyl-3-methylimidazolium and varying anions (chloride and hexafluorophosphate in one of the mixtures and chloride and trifluoromethanesulfonate in the other) and the third binary mixture was composed of a common anion, trifluoromethanesulfonate and two imidazolium cations with ethyl and octyl side chains. Binary mixtures with common cations are found to be homogeneous.

Effect of spacer chain length on the liquid structure of aqueous dicationic ionic liquid solutions: molecular dynamics studies.

The liquid structure of aqueous solutions of five different imidazolium based gemini dicationic ionic liquids 1,n-bis(3-methylimidazolium-1-yl) alkane bromide (n being the length of the spacer alkyl chain), with propyl, pentyl, octyl, decyl and hexadecyl spacer chains has been studied using atomistic molecular dynamics simulations. While solutions with propyl and pentyl spacers are homogeneous, those with octyl and decyl spacers show spatial heterogeneity. Microscopic inhomogeneity in the bulk solution phase increases with an increase in the length of the spacer chain leading to polydisperse aggregates in the solution with a hexadecyl spacer.

Ionic liquids at nonane-water interfaces: molecular dynamics studies.

The structures of ternary systems with water, nonane, and an ionic liquid, with the ionic liquid placed between water and nonane, have been studied using atomistic molecular dynamics simulations. Three different ionic liquids with 1-n-butyl-3-methylimidazolium cation and bromide, tetrafluoroborate, and trifluoromethanesulfonate anions have been studied. The ionic liquids disperse into the aqueous phase quickly and are solubilized in water within 15 ns to form two equivalent nonane-aqueous ionic liquid interfaces.

Effect of cation asymmetry on the aggregation in aqueous 1-alkyl,3-decylimidazolium bromide solutions: molecular dynamics studies.

Self-assembly of cations in aqueous solutions of 1-alkyl,3-decylimidazolium bromide (with four different alkyl chains, methyl, butyl, heptyl, and decyl chain,) have been studied using atomistic molecular dynamics simulations. Polydisperse aggregates of cations are formed in the solution with alkyl tails in the core and the polar head groups present at the surface of the aggregates. The shape of the aggregates is dictated by the length of the alkyl chain.