Hydration and interfacial water in Nafion membrane probed by transmission infrared spectroscopy

Infrared spectroscopy was applied to probe water inside pores and channels of Nafion membrane exchanged with either proton (H+) or sodium ions (Na+). Transmission measurements were performed on freestanding Nafion 112 (approximately 50 microm thickness) in a cell that enabled adjustment of the relative humidity. Experiments that employed Na+-exchanged Nafion focused on relative humidity environments at or below about 32% generated through the use of humectants. Under these conditions, narrow features in the O-H stretching spectral region near 3650-3720 cm(-1), previously attributed to interfacial water, were detected and matched to bands in vibrational sum frequency (VSF) spectra of water/air, water/organic, and salt-solution/air interfaces. The features correspond to the stretching mode of the "free" OH group of water oriented with one hydrogen atom toward other water molecules and interacting through hydrogen bonding and the other straddling the interface extending into fluorocarbon-rich regions (approximately 3668 cm(-1)) or air-filled segments (approximately 3700 cm(-1)) in the membrane. For membrane exchanged with H+, -SO3- groups were easily shifted to -SO3H as water was removed upon exposure to a few Torr of vacuum at 95 degrees C. In contrast, residual water was retained by membrane exchanged with Na+ after exposure to these conditions for up to 72 h. The permeation of methanol and acetone into Na+-exchanged Nafion 112 was also examined. The C-H and O-H stretching modes of methanol were perturbed in a manner that suggests the polymer disrupts hydrogen bonding interactions within the solvent, similar to the effect it exerts on pure water. For acetone, the C-H stretching modes were not shifted appreciably compared to those of the bulk liquid. However, the carbonyl band was affected, indicating the likely importance of dipolar interactions between solvent molecules and polar groups on the polymer. Control experiments performed with poly(hexafluoropropylene-co-tetrafluoroethylene) (FEP) membrane did not show evidence for water or methanol permeation, which demonstrates the critical role played by the ion-filled channels and pores in facilitating solvent transport within Nafion membrane.     

拉曼光谱研究CaCl2和MgCl2对水结构的影响

测试了CaCl2、MgCl2溶液(浓度小于1.0 mol•L-1)的OH伸缩振动区域的拉曼光谱.对所得到的拉曼光谱进行了计算机去卷积处理,并由此计算了不同溶液中水的四面体结构的百分数.研究表明,CaCl2、MgCl2对水中四面体结构有破坏作用，且CaCl2的破坏作用比MgCl2大.与17O核磁共振结果对比与分析,认为CaCl2、MgCl2虽然破坏水中的四面体结构,但通过促进含氢键数少的水分子形成氢键,故从总体上促进水的缔合结构.     

盐对甲醇微观结构的影响

利用拉曼光谱研究盐对甲醇微观结构的影响.比较了不同盐/甲醇体系的O—H伸缩谱段和C—O伸缩谱段的超额拉曼光谱,对比给出了阴、阳离子与甲醇的相互作用.O—H伸缩谱段的超额拉曼光谱明显地显示了阴离子与甲醇形成弱氢键,氢键强度排序为CH3OH-CH3OHCl--CH3OHNO3--CH3OHClO4--CH3OH,在这个波段内,基本观察不到阳离子与甲醇的相互作用.在C—O伸缩谱段内,阴阳离子均有显著的体现,且与它们作用的甲醇C—O伸缩振动频率有如下的关系:CH3—OH(阴离子)CH3—OH(体相)CH3—OH(阳离子).根据C—O伸缩谱段的超额拉曼光谱,拟合了该谱段的拉曼光谱,由分解的谱峰强度得到阴、阳离子第一溶剂化层中甲醇分子的数目,结果显示在该浓度(～0.005)下离子对第一溶剂化层以外的甲醇氢键网络结构没有明显影响.     

Infrared photodissociation spectroscopy of Al(+)(CH(3)OH)(n) (n = 1-4)

Infrared photodissociation spectra of Al(+)(CH(3)OH)(n) (n = 1-4) and Al(+)(CH(3)OH)(n)-Ar (n = 1-3) were measured in the OH stretching region, 3000-3800 cm(-1). For n = 1 and 2, sharp absorption bands were observed in the free OH stretching region, all of which were well reproduced by the spectra calculated for the solvated-type geometry with no hydrogen bond. For n = 3 and 4, there were broad vibrational bands in the energy region of hydrogen-bonded OH stretching vibrations, 3000-3500 cm(-1). Energies of possible isomers for the Al(+)(CH(3)OH)(3),4 ions with hydrogen bonds were calculated in order to assign these bands. It was found that the third and fourth methanol molecules form hydrogen bonds with methanol molecules in the first solvation shell, rather than a direct bonding with the Al(+) ion. For the Al(+)(CH(3)OH)(n) clusters with n = 1-4, we obtained no evidence of the insertion reaction, which occurs in Al(+)(H(2)O)(n). One possible explanation of the difference between these two systems is that the potential energy barriers between the solvated and inserted isomers in the Al(+)(CH(3)OH)(n) system is too high to form the inserted-type isomers.     

Proton transfer and the mobilities of the H+ and OH- ions from studies of a dissociating model for water

Hydrogen (H(+)) and hydroxide (OH(-)) ions in aqueous solution have anomalously large diffusion coefficients, and the mobility of the H(+) ion is nearly twice that of the OH(-) ion. We describe molecular dynamics simulations of a dissociating model for liquid water based on scaling the interatomic potential for water developed by Ojama?e-Shavitt-Singer from ab initio studies at the MP2 level. We use the scaled model to study proton transfer that occurs in the transport of hydrogen and hydroxide ions in acidic and basic solutions containing 215 water molecules. The model supports the Eigen-Zundel-Eigen mechanism of proton transfer in acidic solutions and the transient hyper-coordination of the hydroxide ion in weakly basic solutions at room temperature. The free energy barriers for proton transport are low indicating significant proton delocalization accompanying proton transfer in acidic and basic solutions. The reorientation dynamics of the hydroxide ion suggests changes in the proportions of hyper-coordinated species with temperature. The mobilities of the hydrogen and hydroxide ions and their temperature dependence between 0 and 50 °C are in excellent agreement with experiment and the reasons for the large difference in the mobilities of the two ions are discussed. The model and methods described provide a novel approach to studies of liquid water, proton transfer, and acid-base reactions in aqueous solutions, channels, and interfaces.     

Polarization and experimental configuration analyses of sum frequency generation vibrational spectra, structure, and orientational motion of the air/water interface

Here we report a detailed study on spectroscopy, structure, and orientational distribution, as well as orientational motion, of water molecules at the air/water interface, investigated with sum frequency generation vibrational spectroscopy (SFG-VS). Quantitative polarization and experimental configuration analyses of the SFG data in different polarizations with four sets of experimental configurations can shed new light on our present understanding of the air/water interface. Firstly, we concluded that the orientational motion of the interfacial water molecules can only be in a limited angular range, instead of rapidly varying over a broad angular range in the vibrational relaxation time as suggested previously. Secondly, because different vibrational modes of different molecular species at the interface has different symmetry properties, polarization and symmetry analyses of the SFG-VS spectral features can help the assignment of the SFG-VS spectra peaks to different interfacial species. These analyses concluded that the narrow 3693 cm(-1) and broad 3550 cm(-1) peaks belong to C(infinityv) symmetry, while the broad 3250 and 3450 cm(-1) peaks belong to the symmetric stretching modes with C2v symmetry. Thus, the 3693 cm(-1) peak is assigned to the free OH, the 3550 cm(-1) peak is assigned to the singly hydrogen-bonded OH stretching mode, and the 3250 and 3450 cm(-1) peaks are assigned to interfacial water molecules as two hydrogen donors for hydrogen bonding (with C2v symmetry), respectively. Thirdly, analysis of the SFG-VS spectra concluded that the singly hydrogen-bonded water molecules at the air/water interface have their dipole vector directed almost parallel to the interface and is with a very narrow orientational distribution. The doubly hydrogen-bonded donor water molecules have their dipole vector pointing away from the liquid phase.     

IR spectroscopy on isolated Co(n)(alcohol)m cluster anions (n=1-4, m=1-3): structures and spin states

Isolated cobalt-alcohol cluster anions containing n=1-4 cobalt and m=1-3 alcohol molecules (alcohol=methanol, ethanol, propanol) are produced in a supersonic beam by using a laser ablation source. By applying IR photodissociation spectroscopy vibrational spectra in the OH stretching region are obtained. Several structures in different spin states are discussed for the (n,m) clusters. In comparison with density functional theory calculations applied to both the Co/alcohol clusters and the naked Co cluster anions, an unambiguous structural assignment is achieved. It turns out that structures are preferred with a maximum number of hydrogen bonds between the OH groups and the Co···Co units. These hydrogen bonds are typical for anionic species leading to an activation of the OH groups which is indicated by large red-shifts of the OH stretching frequencies compared to the naked alcohols. For each (n,m) cluster, the frequency shifts systematically with respect to the different alcohols, but the type of structure is identical for all alcohol ligands. The application of IR spectroscopy turns out to be an ideal tool not only as a probe for structures but also for spin states which significantly influence the predicted OH stretching frequencies.     

Infrared spectroscopy of hydrogen-bonded 2-fluoropyridine-water clusters in supersonic jets

The hydrogen-bonded clusters of 2-fluoropyridine with water were studied experimentally in a supersonic free jet and analyzed with molecular orbital calculations. The IR spectra of 2-fluoropyridine-(H2O)(n) (n = 1 to 3) clusters were observed with a fluorescence detected infrared depletion (FDIR) technique in the OH and CH stretching vibrational regions. The frequencies of OH stretching vibrations show that water molecules bond to the nitrogen atom of 2-fluoropyridine in the clusters. The hydrogen-bond formation between aromatic CH and O was evidenced in the 1:2 and 1:3 clusters from the experimental and calculated results. The overtone vibrations of the OH bending mode in hydrogen-bonded water molecules appear in the IR spectra, and these frequencies become higher with the increase of the number of water molecules in the clusters. The band structure of the IR spectra in the CH stretching region changes depending on the number of coordinating water molecules.     

Air-liquid interfaces of aqueous solutions containing ammonium and sulfate: spectroscopic and molecular dynamics studies

Investigations of the air-liquid interface of aqueous salt solutions containing ammonium (NH(4)(+)) and sulfate (SO(4)(2-)) ions were carried out using molecular dynamics simulations and vibrational sum frequency generation spectroscopy. The molecular dynamics simulations show that the predominant effect of SO(4)(2-) ions, which are strongly repelled from the surface, is to increase the thickness of the interfacial region. The vibrational spectra reported are in the O-H stretching region of liquid water. Isotropic Raman and ATR-FTIR (attenuated total reflection Fourier transform infrared) spectroscopies were used to study the effect of ammonium and sulfate ions on the bulk structure of water, whereas surface sum frequency generation spectroscopy was used to study the effect of these ions on the interfacial structure of water. Analysis of the interfacial and bulk vibrational spectra reveal that aqueous solutions containing SO(4)(2-) perturb the interfacial water structure differently than the bulk and, consistent with the molecular dynamics simulations, reveal an increase in the thickness of the interfacial region.     

Raman spectroscopic study on the structure of water in aqueous solution of alpha,omega-amino acids

The structure and hydrogen bonding of water in an aqueous solution of various alpha,omega-amino acids were analyzed using the contours of the OH stretching in the polarized Raman spectra. From the relative intensity of the collective band (C value) corresponding to a long-range coupling of the OH stretching in the aqueous amino acid solutions, the number of hydrogen bonds disrupted due to the presence of one amino acid molecule (N(corr) value) was evaluated. The N(corr) value for glycine was slightly positive, whereas with an increase in the number of methylene groups between ammonium and carboxylate groups, the N(corr) value gradually increased. These results suggest that the species with proximal anionic and cationic groups do not disturb the hydrogen-bonded network structure of water significantly, probably due to the counteraction of the electrostatic hydration effect attributable to the anionic and cationic groups.     

Effect of hydrogen bonding and cooperativity on stretching force constants of formamide

Stretching force constants for formamide and its seven associated species involving two to four molecules hydrogen-bonded through linear and cyclic configurations and 10 structures containing formamide hydrogen-bonded with one to five water molecules are reported. Since ab initio calculations are rather inconvenient to perform on such big clusters and are time-consuming, CNINDO MO calculations were carried out using the gradient method. The results demonstrate, on the one hand, the feasibility of semiempirical calculations for the evaluation of trends in force constants for big clusters where generally ab initio calculations become much involved and, on the other hand, explain the effect of hydrogen bonding and cooperativity on force constants and vibrational spectra of biologically important systems composed of formamide in the condensed phase and its aqueous solutions. The C?O and N? H stretching force constants are found to reduce significantly on hydrogen bonding. The reduction in force constant is further enhanced when two cyclic dimers become associated through a linear hydrogen bond. The results indicate justification for the stabilization of the formamide structure with two cyclic dimers hydrogen-bonded together. The reduction in the force constants on hydrogen bonding also reflect the cooperativity contribution. The C?O and C? N stretching force constants for the structures corresponding to formamide in liquid and aqueous solution phases are in agreement with the experimental vibrational frequencies reported.     

Hydrogen Bonding in Liquid Water and in the Hydration Shell of Salts

A near‐IR spectral study on pure water and aqueous salt solutions is used to investigate stoichiometric concentrations of different types of hydrogen‐bonded water species in liquid water and in water comprising the hydration shell of salts. Analysis of the thermodynamics of hydrogen‐bond formation signifies that hydrogen‐bond making and breaking processes are dominated by enthalpy with non‐negligible heat capacity effects, as revealed by the temperature dependence of standard molar enthalpies of hydrogen‐bond formation and from analysis of the linear enthalpy–entropy compensation effects. A generalized method is proposed for the simultaneous calculation of the spectrum of water in the hydration shell and hydration number of solutes. Resolved spectra of water in the hydration shell of different salts clearly differentiate hydrogen bonding of water in the hydration shell around cations and anions. A comparison of resolved liquid water spectra and resolved hydration‐shell spectra of ions highlights that the ordering of absorption frequencies of different kinds of hydrogen‐bonded water species is also preserved in the bound state with significant changes in band position, band width, and band intensity because of the polarization of water molecules in the vicinity of ions.     

Pressure response of Raman spectra of water and its implication to the change in hydrogen bond interaction

In situ Raman spectroscopic measurements of water in the region of OH vibration were conducted up to 0.4 GPa at 23 and 52 degrees C. The frequencies of the decomposed OH stretching bands initially decreased with increasing pressure, reached a minimum at 0.15 GPa and increased up to 0.3 GPa and then decreased, which corresponds to the variations of the strength of hydrogen bonding. This variation was observed at 23 degrees C, but not at 52 degrees C, which suggests a change in pressure dependence on the hydrogen bond interaction between these two temperatures. Based on the equilibration model between hydrogen-bonded and nonhydrogen-bonded molecules, the present experimental results indicate that the pressure variation of the viscosity depends on the ratio of hydrogen-bonded molecules, rather than the strength of hydrogen bonding between molecules.     

The spectroscopic signature of the "all-surface" to "internally solvated" structural transition in water clusters in the n = 17-21 size regime

The existence of a transitional size regime where preferential stabilization alternates between "all-surface" (all atoms on the surface of a cluster) and "internally solvated" (one water molecule at the center of the cluster, fully solvated) configurations with the addition or the removal of a single water molecule, predicted earlier with the flexible, polarizable (many-body) Thole-type model interaction potential (TTM2-F), has been confirmed from electronic structure calculations for (H2O)n, n = 17-21. The onset of the appearance of the first "interior" configuration in water clusters occurs for n = 17. The observed structural alternation between interior (n = 17, 19, 21) and all-surface (n = 18, 20) global minima in the n = 17-21 cluster regime is accompanied by a corresponding spectroscopic signature, namely, the undulation in the position of the most redshifted OH stretching vibrations according to the trend: interior configurations exhibit more redshifted OH stretching vibrations than all-surface ones. These most redshifted OH stretching vibrations form distinct groups in the intramolecular region of the spectra and correspond to localized vibrations of donor OH stretches that are connected to neighbors via "strong" (water dimer-like) hydrogen bonds and belong to a water molecule with a "free" OH stretch.     

New thermochemical parameter for describing solvent effects on IR stretching vibration frequencies. Communication 1. Assessment of van der Waals interactions

Solvent effects on OH stretching vibrations in several complexes with hydrogen bonding have been investigated by FTIR spectroscopy. To assess the influence of van der Waals (vdW) interactions on frequency shifts, a new parameter of solvent, square root deltacavhS, is proposed. This parameter has been derived from equations describing enthalpy of non-specific solvation. Linear correlation was established between the OH frequency shift (with respect to the gas phase) and parameter square root deltacavhS for a series of complexes of aliphatic alcohols with standard proton acceptors. Linear correlations with square root deltacavhS were also observed for a series of "free" O-H and also C=O, P=O, S=O and C-Br stretching vibrations. A new method is proposed for estimating the gas-phase stretching frequency from IR spectra of solutions. In addition, frequencies of "free" X-H groups in neat bases were deduced from the experimental data.     

Theoretical study of the changes in the vibrational characteristics arising from the hydrogen bonding between Vitamin C (L-ascorbic acid) and H2O

The vibrational characteristics (vibrational frequencies, infrared intensities and Raman activities) for the hydrogen-bonded system of Vitamin C (L-ascorbic acid) with five water molecules have been predicted using ab initio SCF/6-31G(d,p) calculations and DFT (BLYP) calculations with 6-31G(d,p) and 6-31++G(d,p) basis sets. The changes in the vibrational characteristics from free monomers to a complex have been calculated. The ab initio and BLYP calculations show that the complexation between Vitamin C and five water molecules leads to large red shifts of the stretching vibrations for the monomer bonds involved in the hydrogen bonding and very strong increase in their IR intensity. The predicted frequency shifts for the stretching vibrations from Vitamin C taking part in the hydrogen bonding are up to -508 cm(-1). The magnitude of the wavenumber shifts is indicative of relatively strong OH...H hydrogen-bonded interactions. In the same time the IR intensity and Raman activity of these vibrations increase upon complexation. The IR intensity increases dramatically (up to 12 times) and Raman activity increases up to three times. The ab initio and BLYP calculations show, that the symmetric OH vibrations of water molecules are more sensitive to the complexation. The hydrogen bonding leads to very large red shifts of these vibrations and very strong increase in their IR intensity. The asymmetric OH stretching vibrations of water, free from hydrogen bonding are less sensitive to the complexation than the hydrogen-bonded symmetric OH stretching vibrations. The increases of the IR intensities for these vibrations are lower and red shifts are negligible.     

Proton/Hydrogen‐Transfer Coordinate of 2,5‐Dihydroxybenzoic Acid Investigated in a Supersonic Beam: Combined IR/UV Spectroscopy in the S0, S1, and D0 States

As a model system for intramolecular proton/hydrogen‐transfer coordinates, the structure of 2,5‐dihydroxybenzoic acid is investigated for the ground, first electronically excited and also the ionic state. Combined IR/UV spectroscopy in molecular‐beam experiments is applied and the experimental results are interpreted by the application of DFT and CASPT2 methods. No proton or hydrogen transfer is observed, but evidence is given for a hydrogen dislocation of the intramolecular hydrogen bond in the S₁ state and to lesser extent in the D₀ state. To obtain direct information on the proton/hydrogen‐transfer coordinate, IR spectra are recorded both in the region of the OH and especially the CO stretching vibrations by also applying two new variants of combined IR/UV spectroscopy for the S₁ and D₀ states. The CO groups are directly involved in the hydrogen bond and, in contrast to the hydrogen‐bonded OH groups, the CO stretching frequencies can be observed in all electronic states.     

Connecting structure to infrared spectra of molecular and autodissociated HCl--water aggregates

The properties of perdeuterated HCl(H2O)n aggregates with n=1, 2, ..., 6 water molecules are studied by means of ab initio molecular dynamics simulations. The specific focus is on the phenomenon of autodissociation of the acid HCl as a function of the microsolvation environment size. The calculations provide a basis for characterization in terms of autodissociation energetics as well as in terms of the impact of thermal fluctuations on structure including proton fluxionality and in terms of anharmonic infrared vibrational spectra. Structure stabilization is dominated by strong hydrogen bonds resulting in distinct topologies, which, in turn, heavily influence acid dissociation. The latter is favored for the first time when n = 4. In that case, three hydrogen bonds can be donated toward the chlorine while at the same time a hydronium core is perfectly solvated according to the eigencomplex motif. Hydrogen-bonding interactions between DCl and its solvating molecules affect the dynamical behavior of the D-Cl bond significantly. This can be seen by the onset of fluxionality and an emerging tendency toward proton transfer for the larger clusters. Connecting IR spectra to structural information is possible by exploiting the following observations. Zwitterionic species show characteristic differences in the hydronium region, whereas the D-Cl stretching regime is useful to distinguish neutral aggregates. Furthermore, in the case of fluxional protons large-amplitude motion leads to characteristic band shifts and significant band broadening effects.     

Solvation dynamics in Ni+ (H2O)n clusters probed with infrared spectroscopy

Infrared photodissociation spectroscopy is reported for mass-selected Ni+ (H2O)n complexes in the O-H stretching region up to cluster sizes of n = 25. These clusters fragment by the loss of one or more intact water molecules, and their excitation spectra show distinct bands in the region of the symmetric and asymmetric stretches of water. The first evidence for hydrogen bonding, indicated by a broad band strongly red-shifted from the free OH region, appears at the cluster size of n = 4. At larger cluster sizes, additional red-shifted structure evolves over a broader wavelength range in the hydrogen-bonding region. In the free OH region, the symmetric stretch gradually diminishes in intensity, while the asymmetric stretch develops into a closely spaced doublet near 3700 cm(-1). The data indicate that essentially all of the water molecules are in a hydrogen-bonded network by the size of n = 10. However, there is no evidence for the formation of clathrate structures seen recently via IR spectroscopy of protonated water clusters.