Maciej Śmiechowski

Hydration of simple amides. FTIR spectra of HDO and theoretical studies.

The hydration of formamide (F), N-methylformamide (NMF), N,N-dimethylformamide (DMF), acetamide (A), N-methylacetamide (NMA), and N,N-dimethylacetamide (DMA) has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure has been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To facilitate the interpretation of obtained spectral results, DFT calculations of aqueous amide clusters were performed. Molecular dynamics (MD) simulation for the cis and trans forms of NMA was also carried out for the SPC model of water. Infrared spectra reveal that only two to three water molecules from the surrounding of the amides are statistically affected, from among ca. 30 molecules present in the first hydration sphere. The structural-energetic characteristic of these solute-affected water molecules differs only slightly from that in the bulk and corresponds to the clathrate-like hydrogen-bonded cage typical for hydrophobic hydration, with the possible exception of F. MD simulations confirm such organization of water molecules in the first hydration sphere of NMA and indicate a practical lack of orientation and energetic effects beyond this sphere. The geometry of hydrogen-bonded water molecules in the first hydration sphere is very similar to that in the bulk phase, but MD simulations have affirmed subtle differences recognized by the spectral method and enabled their understanding. The spectral data and simulations results are highly compatible. In the case of F, NMF, and A, there is a visible spectral effect of water interactions with N-H groups, which have destabilizing influence on the amides hydration shell. There is no spectral sign of such interaction for NMA as the solute. The energetic stability of water H-bonds in the amide hydration sphere and in the bulk fulfills the order: NMA > DMA > A > NMF > bulk > DMF > F. Microscopic parameters of water organization around the amides obtained from the spectra, which have been used in the hydration model based on volumetric data, confirm the more hydrophobic character of the first three amides in this sequence. The increased stability of the hydration sphere of NMA relative to DMA and of NMF relative to DMF seems to have its origin in different geometries, and so the stability, of water cages containing the amides.

Vibrational spectroscopy of semiheavy water (HDO) as a probe of solute hydration

Vibrational spectroscopy is an ideally suited tool for the study of solute hydration. Nevertheless, water is commonly considered by spectroscopists a difficult solvent to work with. However, by using the isotopic dilution technique, in which a small amount of D2O is introduced into H2O or vice versa with formation of semiheavy water (HDO), many technical and interpretative problems connected with measurement of infrared spectra of water may be circumvented. Particularly, the isotopic decoupling of stretching vibrational modes greatly simplifies interpretation of the spectra. Systematic studies conducted in several laboratories since the 1980s up to the present day have provided a vast amount of data, concerning mainly ionic hydration. Many of these experiments have been performed in our laboratory. The analysis method we applied is based on the quantitative version of the difference spectra technique and allows separation of the spectrum of solute-affected HDO from the bulk solvent. This review illustrates the development of vibrational spectroscopy of HDO and spectral analysis methods over the years, as well as summarizes the results obtained for ionic and nonionic solutes, including some general hydration models formulated on their basis.

Intramolecular interactions in crystals of tris(2,6-diisopropylphenoxy)silanethiol and its sodium salts.

Hydrolytically stable silanethiol tris(2,6-diisopropylphenoxy)silanethiol (TDST) has been synthesized and reacted with sodium metal. In solid state TDST exhibits π-interactions between the S-H unit and the π-system of the arene, replaced by cation-π interactions in its sodium salts. The interactions are documented by crystal structures and FT-IR spectroscopy.

Spatial decomposition and assignment of infrared spectra of simple ions in water from mid-infrared to THz frequencies: Li+(aq) and F−(aq)

Ionic hydration is of fundamental relevance from chemical reactivity in aqueous solution to biomolecular function at physiological conditions. Vibrational spectroscopy belongs to the most widely used experimental methods in studies of solvation phenomena. There is, however, still limited molecular understanding as to how the vibrational response of solutions is modulated by the presence of solvation shells around solutes, i.e., by interfacial water. Liquid-state THz spectroscopy has been demonstrated to be able to detect even small solute-induced changes of the hydrogen bond dynamics at the solute-water interface. In many cases it reveals rather long-ranged dynamical correlations around solutes, involving many solvent molecules, that can be tackled theoretically by analyzing vibrational spectra in a distance-resolved manner. Here, several spatial decomposition schemes for infrared spectra are used to reveal the distinct distance- and frequency-dependent contributions of the solvation shells to the spectral response in aqueous solutions of Li(+) and F(-). The importance of an explicit representation of the solutes electronic structure for the proper description of solute-solvent polarization effects is demonstrated. The solvents response to the presence of the solute is systematically disentangled and reveals important differences between the spectral responses due to intra- and intermolecular motion as probed in the mid- and far-infrared spectral windows, respectively.

Correlated Particle Motion and THz Spectral Response of Supercritical Water.

Molecular dynamics simulations of supercritical water reveal distinctly different distance-dependent modulations of dipolar response and correlations in particle motion compared to ambient conditions. The strongly perturbed H-bond network of water at supercritical conditions allows for considerable translational and rotational freedom of individual molecules. These changes give rise to substantially different infrared spectra and vibrational density of states at THz frequencies for densities above and below the Widom line that separates percolating liquidlike and clustered gaslike supercritical water.

Anion–water interactions of weakly hydrated anions: molecular dynamics simulations of aqueous NaBF4 and NaPF6

ABSTRACT In aqueous ionic solutions, both the structure and the dynamics of water are altered dramatically with respect to the pure solvent. The emergence of novel experimental techniques makes these changes accessible to detailed investigations. At the same time, computational studies deliver unique possibilities for the interpretation of the experimental data at the molecular level. Here, using molecular dynamics simulations, we demonstrate how competing mechanisms can explain the seemingly contradictory statements about the structure and dynamics of ion-coordinated solvent in aqueous solutions of two interesting and technologically important electrolytes, NaBF4 and NaPF6. While the static structural data (i.e. radial, radial-angular and spatial distribution functions, as well as hydrogen bonding statistics) unequivocally point at very weak anion–water hydrogen bonding in both salts, dynamic analyses (in particular, orientational anisotropy decay and solvent residence times) reveal quite significant retardation of water rotation and mobility due to solute coordination. Additionally, rotational immobilisation of coordinated solvent molecules is clearly unrelated to the hydrogen bond strength between them, as demonstrated by the interatomic oxygen–oxygen distance distributions for coordinated and bulk water.

Molecular hydrogen solvated in water – A computational study

The aqueous hydrogen molecule is studied with molecular dynamics simulations at ambient temperature and pressure conditions, using a newly developed flexible and polarizable H2 molecule model. The design and implementation of this model, compatible with an existing flexible and polarizable force field for water, is presented in detail. The structure of the hydration layer suggests that first-shell water molecules accommodate the H2 molecule without major structural distortions and two-dimensional, radial-angular distribution functions indicate that as opposed to strictly tangential, the orientation of these water molecules is such that the solute is solvated with one of the free electron pairs of H2O. The calculated self-diffusion coefficient of H2(aq) agrees very well with experimental results and the time dependence of mean square displacement suggests the presence of caging on a time scale corresponding to hydrogen bond network vibrations in liquid water. Orientational correlation function of H2 experiences an extremely short-scale decay, making the H2-H2O interaction potential essentially isotropic by virtue of rotational averaging. The inclusion of explicit polarizability in the model allows for the calculation of Raman spectra that agree very well with available experimental data on H2(aq) under differing pressure conditions, including accurate reproduction of the experimentally noted trends with solute pressure or concentration.

Unusual Influence of Fluorinated Anions on the Stretching Vibrations of Liquid Water

Infrared (IR) spectroscopy is a commonly used and invaluable tool in the studies of solvation phenomena in aqueous solutions. Concurrently, ab initio molecular dynamics (AIMD) simulations deliver the solvation shell picture at a molecular detail level and allow for a consistent decomposition of the theoretical IR spectrum into underlying spatial correlations. Here, we demonstrate how the novel spectral decomposition techniques can extract important information from the computed IR spectra of aqueous solutions of BF4- and PF6-, interesting weakly coordinating anions that have been known for a long time to alter the IR spectrum of water in an unusual manner. The distance-dependent spectra of both ions are analyzed using the spectral similarity method that provides a quantitative picture of both the spectrum of the solute-affected solvent and the number of solvent molecules thus altered. We find, in accordance with previous experiments, a considerable blue shift of the νOH stretching band of liquid water by 264 cm-1 for BF4- and 306 cm-1 for PF6-, with the affected numbers being 3.7 and 4.2, respectively. Considering also the additional information on solute-solvent dipolar couplings delivered by radially and spatially resolved IR spectra, the computational IR spectroscopy based on AIMD simulations is shown to be a viable predictive tool with strong interpretative power.

Visualizing spatially decomposed intermolecular correlations in the infrared spectra of aprotic liquids

Infrared (IR) spectroscopy is commonly used to study intermolecular interactions in the liquid phase, including solvation phenomena. On the other hand, ab initio molecular dynamics (AIMD) simulations offer the possibility to obtain IR spectra from first principles. Surpassing the experiment, AIMD simulations can deliver additional information on the spatial intermolecular correlations underlying the IR spectrum of the liquid. Although such correlations contribute significantly to the IR spectra of associated liquids, such as water, they are equally important in the case of aprotic solvents, where dipole-dipole interactions are dominant. Here, the extent and non-trivial character of the spatial correlations in the IR spectra are demonstrated on the example of γ-butyrolactone (GBL), an important solvent in the rechargeable cell industry.