Ion/Water Network Structural Dynamics in Highly Concentrated Lithium Chloride and Lithium Bromide Solutions Probed with Ultrafast Infrared Spectroscopy.

The structural dynamics of highly concentrated LiCl and LiBr aqueous solutions were observed from 1-4 to 1-16 water molecules per ion pair using ultrafast polarization-selective pump-probe (PSPP) experiments on the OD stretch of dilute HOD. At these high salt concentrations, an extended ion/water network exists with complex structural dynamics. Population decays from PSPP experiments highlight two distinct water components. From the frequency-dependent amplitudes of the decays, the spectra of hydroxyls bound to halides and to water oxygens are obtained, which are not observable in the FT-IR spectra. PSPP experiments also measure frequency-dependent water orientational relaxation. At short times, wobbling dynamics within a restricted angular cone occurs. At high concentrations, the cone angles are dependent on frequency (hydrogen bond strength), but at higher water concentrations (>10 waters per ion pair), there is no frequency dependence. The average cone angle increases as the ion concentration decreases. The slow time constant for complete HOD orientational relaxation is independent of concentration but slower in LiCl than in LiBr. Comparison to structural MD simulations of LiCl from the literature indicates that the loss of the cone angle wavelength dependence and the increase in the cone angles as the concentration decreases occur as the prevalence of large ion/water clusters gives way to contact ion pairs.

Water Dynamics in Aqueous Poly-N-Isopropylacrylamide Below and Through the Lower Critical Solution Temperature.

Poly-N-isopropylacrylamide (PNIPAM) is a thermo-responsive polymer that exhibits a reversible structural change from extended chains to aggregates in aqueous solution above its lower critical solution temperature (LCST). Using polarization-selective IR pump-probe spectroscopy, the water orientational dynamics in PNIPAM from below to above the LCST were examined and compared to those of its monomer solution, N-isopropylacrylamide (NIPAM), polyacrylamide, and an acrylamide monomer solution, which are not thermo-responsive. The OD stretch of dilute HOD in H2O is used as a vibrational probe of water orientational dynamics. Below the LCST of the polymer, NIPAM and PNIPAM solutions exhibited identical water dynamics that were significantly different from those of bulk water, containing both faster and slower components due to solute-water interactions. Therefore, there is no difference in the nature of water interactions with a single NIPAM moiety and a long polymer chain. For all systems, including PNIPAM below and above the LCST, the orientational dynamics were modeled with a bulk water component and a polymer/monomer-associated component based on previous experimental and computational findings. Above the LCST, PNIPAM showed fast water orientational relaxation but much slower long-time dynamics compared to those of NIPAM. The slow component in PNIPAM, which was too slow to be accurately measured due to the limited OD vibrational lifetime, is ascribed to water confined in small voids (<2 nm in diameter) of PNIPAM globules. These results highlight important details about thermo-responsive polymers and the dynamics of their solvation water as they undergo a significant structural change.

Water Dynamics and Structure of Highly Concentrated LiCl Solutions Investigated Using Ultrafast Infrared Spectroscopy.

In highly concentrated salt solutions, the water hydrogen bond (H-bond) network is completely disrupted by the presence of ions. Water is forced to restructure as dictated by the water-ion and ion-ion interactions. Using ultrafast polarization-selective pump-probe (PSPP) spectroscopy measurements of the OD stretch of dilute HOD, we demonstrate that the limited water-water H-bonding present in concentrated lithium chloride solutions (up to four waters per ion pair) is, on average, stronger than that occurring in bulk water. Furthermore, information on the orientational dynamics and the angular restriction of water H-bonded to both water oxygens and chloride anions was obtained through analysis of the frequency-dependent anisotropy decays. It was found that, when the salt concentration increased, the water showed increasing restriction and slowing at frequencies correlated with strong H-bonding. The angular restriction of the water molecules and strengthening of water-water H-bonds are due to the formation of a water-ion network not present in bulk water and dilute salt solutions. The structural evolution of the ionic medium was also observed through spectral diffusion of the OD stretch using 2D IR spectroscopy. Compared to bulk water, there is significant slowing of the biexponential spectral diffusion dynamics. The slowest component of the spectral diffusion (13 ps) is virtually identical to the time for complete reorientation of HOD measured with the PSPP experiments. This result suggests that the slowest component of the spectral diffusion reflects rearrangement of water molecules in the water-ion network.

Hydration and Hydrogen Bond Order of Octadecanoic Acid and Octadecanol Films on Water at 21 and 1 °C.

The temperature-dependent hydration structure of long-chain fatty acids and alcohols at air-water interfaces has great significance in the fundamental interactions underlying ice nucleation in the atmosphere. We present an integrated theoretical and experimental study of the temperature-dependent vibrational structure and electric field character of the immediate hydration shells of fatty alcohol and acid headgroups. We use a combination of surface-sensitive infrared reflection-absorption spectroscopy (IRRAS), surface potentiometry, and ab initio molecular dynamics simulations to elucidate detailed molecular structures of the octadecanoic acid and octadecanol (stearic acid and stearyl alcohol) headgroup hydration shells at room temperature and near freezing. In experiments, the alcohol at high surface concentration exhibits the largest surface potential; yet we observe a strengthening of the hydrogen-bonding for the solvating water molecules near freezing for both the alcohol and the fatty acid IRRAS experiments. Results reveal that the hydration shells for both compounds screen their polar headgroup dipole moments reducing the surface potential at low surface coverages; at higher surface coverage, the polar headgroups become dehydrated, which reduces the screening, correlating to higher observed surface potential values. Lowering the temperature promotes tighter chain packing and an increase in surface potential. IRRAS reveals that the intra- and intermolecular vibrational coupling mechanisms are highly sensitive to changes in temperature. We find that intramolecular coupling dominates the vibrational relaxation pathways for interfacial water determined by comparing the H2O and the HOD spectra. Using ab initio molecular dynamics (AIMD) calculations on cluster systems of propanol + 6H2O and propionic acid + 10H2O, a spectral decomposition scheme was used to correlate the OH stretching motion with the IRRAS spectral features, revealing the effects of intra- and intermolecular coupling on the spectra. Spectra calculated with AIMD reproduce the red shift and increase in intensity observed in experimental spectra corresponding to the OH stretching region of the first solvation shell. These findings suggest that intra- and intermolecular vibrational couplings strongly impact the OH stretching region at fatty acid and fatty alcohol water interfaces. Overall, results are consistent with ice templating behavior for both the fatty acid and the alcohol, yet the surface potential signature is strongest for the fatty alcohol. These findings develop a better understanding of the complex surface potential and spectral signatures involved in ice templating.

Vibrational exciton delocalization precludes the use of infrared intensities as proxies for surfactant accumulation on aqueous surfaces.

Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but vibrational coupling between surfactant molecules can manifest as signal depletion in one-dimensional spectra. Through a combination of experiment and theory, we demonstrate the emergence of vibrational exciton delocalization in infrared reflection-absorption spectra of soluble and insoluble surfactants at the air/water interface. Vibrational coupling causes a significant decrease in peak intensities corresponding to C-F vibrational modes of perfluorooctanoic acid molecules. Vibrational excitons also form between arachidic acid surfactants within a compressed monolayer, manifesting as signal reduction of C-H stretching modes. Ionic composition of the aqueous phase impacts surfactant intermolecular distance, thereby modulating vibrational coupling strength between surfactants. Our results serve as a cautionary tale against employing alkyl and fluoroalkyl vibrational peak intensities as proxies for concentration, although such analysis is ubiquitous in interface science.

Calcium bridging drives polysaccharide co-adsorption to a proxy sea surface microlayer.

Saccharides comprise a significant mass fraction of organic carbon in sea spray aerosol (SSA), but the mechanisms through which saccharides are transferred from seawater to the ocean surface and eventually into SSA are unclear. It is hypothesized that saccharides cooperatively adsorb to other insoluble organic matter at the air/sea interface, known as the sea surface microlayer (SSML). Using a combination of surface-sensitive infrared reflection-absorption spectroscopy and all-atom molecular dynamics simulations, we demonstrate that the marine-relevant, anionic polysaccharide alginate co-adsorbs to an insoluble palmitic acid monolayer via divalent cationic bridging interactions. Ca2+ induces the greatest extent of alginate co-adsorption to the monolayer, evidenced by the ∼30% increase in surface coverage, whereas Mg2+ only facilitates one-third the extent of co-adsorption at seawater-relevant cation concentrations due to its strong hydration propensity. Na+ cations alone do not facilitate alginate co-adsorption, and palmitic acid protonation hinders the formation of divalent cationic bridges between the palmitate and alginate carboxylate moieties. Alginate co-adsorption is largely confined to the interfacial region beneath the monolayer headgroups, so surface pressure, and thus monolayer surface coverage, only changes the amount of alginate co-adsorption by less than 5%. Our results provide physical and molecular characterization of a potentially significant polysaccharide enrichment mechanism within the SSML.