Hydrated anion clusters

Figure 8 (see color section). Structures of hydrated anion clusters. 

Figure 13.15 An ionic atmosphere model for non ideal behavior of electrolyte solutions. Hydrated anions cluster near cations, and vice versa, to form ionic atmospheres of net opposite charge. Because the ions do not act independently, their concentrations are effectively /ess than expected. Such interactions cause deviations from ideal behavior.

Wallace, W.T., Wyrwas, R.B., Whetten, R.L., Mitric, R. and Bonadc-Kouteck, V. (2003) Oxygen adsorption on hydrated gold cluster anions experiment and theory. Journal of the American Chemical Society, 125, 8408-8414. 

In this chapter, the recent progress in the understanding of the nature and dynamics of excess (solvated) electrons in molecular fluids composed of polar molecules with no electron affinity (EA), such as liquid water (hydrated electron, and aliphatic alcohols, is examined. Our group has recently reviewed the literature on solvated electron in liquefied ammonia and saturated hydrocarbons and we refer the reader to these publications for an introduction to the excess electron states in such liquids. We narrowed this review to bulk neat liquids and (to a much lesser degree) large water anion clusters in the gas phase that serve as useful reference systems for solvated electrons in the bulk. The excess electrons trapped by supramolecular structures (including single macrocycle molecules ), such as clusters of polar molecules and water pools of reverse micelles in nonpolar liquids and complexes of the electrons with cations in concentrated salt solutions, are examined elsewhere. 

This narrative echoes the themes addressed in our recent review on the properties of uncommon solvent anions. We do not pretend to be comprehensive or inclusive, as the literature on electron solvation is vast and rapidly expanding. This increase is cnrrently driven by ultrafast laser spectroscopy studies of electron injection and relaxation dynamics (see Chap. 2), and by gas phase studies of anion clusters by photoelectron and IR spectroscopy. Despite the great importance of the solvated/ hydrated electron for radiation chemistry (as this species is a common reducing agent in radiolysis of liquids and solids), pulse radiolysis studies of solvated electrons are becoming less frequent perhaps due to the insufficient time resolution of the method (picoseconds) as compared to state-of-the-art laser studies (time resolution to 5 fs ). The welcome exceptions are the recent spectroscopic and kinetic studies of hydrated electrons in supercriticaF and supercooled water. As the theoretical models for high-temperature hydrated electrons and the reaction mechanisms for these species are still rmder debate, we will exclude such extreme conditions from this review. 

Thus, cation water clusters favour internal structures in contrast to the surface strucmres favoured by anionic water clusters. This critical difference in the structural preferences of hydrated cation and anion clusters provides important cues for the design of cation- and anion-specific ionophores and receptors. Indeed, we note that most cation receptors have spherical structures, while almost all anion receptors do not have compact spherical structures but have a vacant space around the anion binding site without full coordination (which might be exceptional for the F ion with strong electronegativity for which the excess electron is strongly bound to F due to its small ion radius). However, as the temperature increases, the hydration structure tends to be more spherical due to entropy effects. 

Dioxide dihydrates and heteropolyacid hydrates, HPA (see Chapter 18), are representative examples. Following reference 5, in Sn02-2H20 (c 25 c = [Pg.9]

Experimental and computational study of hydration reactions of aluminum oxide anion clusters ... 

L. D. Jacobson andj. M. Herbert,/. Am. Ghem. Soc., 133,19889-19899 (2011). Theoretical Characterization of Four Distinct Isomer Types in Hydrated-Electron Clusters, and Proposed Assignments for Photoelectron Spectra of Water Cluster Anions. 

A possible explanation comes from X-ray analyses of the sulfonic acids [45]. All X-rayed crown ether crystals contained water and the sulfonic acid moiety was dissociated. Therefore in crystals of [45], macrocyclic ben-zenesulfonate anions and hydronium ions (sometimes hydrated) are present. The ions are bound to each other by hydrogen bonds. The size of the included water-hydronium ion cluster (varying by the number of solvating water molecules) depends on the ring size. In the 15-membered ring, HsO" was found, whereas in a 21-membered ring HsO and in the 27-membered ring were present. This means the sulfonic acid functions in [45] are... 

By swelling with aqueous electrolyte, cations (and, to lesser extent, also anions) penetrate together with water into the hydrophilic regions and form spherical electrolyte clusters with micellar morphology. The inner surface of clusters and channels is composed of a double layer of the immobilized —SO3 groups and the equivalent number of counterions, M+. Anions in the interior of the clusters are shielded from the —SOJ groups by hydrated cations and water molecules. On the other hand, anions are thus... 

Figure 19. (a) Cluster size dependence of the rate constants for the reactions of CO2 with the large hydrated hydroxyl anions at T= 130 K O, experimental values for OH (H2O), —, calculated values for 0H (H20)n. (b) Dependence of rate constants on cluster size for the reactions of 0H (H20)n with SO2 at T = 135 K. Taken with permission from ref. 19. 

This increase of the mass was ascribed earlier to the adsorption of perchlorate ions, °° a conclusion that found no confirmation in work published later. It turns out that other weakly adsorbing anions of different masses (NOJ, CFySOf) give the same values of frequency decrease as was observed for C104. Ultimately, the increase of the electrode mass in the preoxide region was explained in terms of the three-dimensional hydration of AuOH, which is present in small amounts at the gold surface. The mass increase was consistent with the surface hydration for a cluster of about 32 water molecules per one AuOH site. ... 

In an early study, Mauritz et al. investigated anion—cation interactions within Nation sulfonate membranes versus degree of hydration using FTIR/ ATR and solid state NMR (SSNMR) spectroscopies. An understanding of the dynamic ionic—hydrate molecular structures within and between the sulfonate clusters is essential for a fundamental understanding of the action of these membranes in ion transport. This information can be directly related to the equilibrium water swelling that, in turn, influences molecular migration. 

The last example of a sequential approach is from Sanov (excerpt 130). A series of increasingly complex experiments is proposed to study the photochemistry of 02, and OCS . Sanov begins with the easier diatomic anions (02 and which will serve as prototypes for subsequent experiments. Next, he will study a larger, polyatomic anion (OCS ) and its cluster ions, 0CS (H20)]j. In the future, he will study even larger dimers and trimers (OCS)n (n > 2) and their hydrated counterparts. 

Building on the initial findings described in Section 4, we will acquire photoelectron images of 0CS (H20)i, cluster anions at different wavelengths in the visible and UV and investigate the dynamics of hydration and hydration-induced stabilization of... 

One of the simplest biochemical addition reactions is the hydration of carbon dioxide to form carbonic acid, which is released from the zinc-containing carbonic anhydrase (left, Fig. 13-1) as HC03-. Aconitase (center, Fig. 13-4) is shown here removing a water molecule from isocitrate, an intermediate compound in the citric acid cycle. The H20 that is removed will become bonded to an iron atom of the Fe4S4 cluster at the active site as indicated by the black H20. An enolate anion derived from acetyl-CoA adds to the carbonyl group of oxaloacetate to form citrate in the active site of citrate synthase (right, Fig. 13-9) to initiate the citric acid cycle. 

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