Proton mobility and stability of water clusters containing alkali metal ions

Zatula, Alexey S.; Ryding, Mauritz Johan; Andersson, Patrik; Uggerud, Einar

doi:10.1016/j.ijms.2012.07.017

Cited by 20 publications

(25 citation statements)

References 62 publications

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“…The relative intensities of these peaks do not vary significantly with temperature. These results indicate that clathrate structures are not energetically competitive for Na, consistent with theory, 12,45,46 the absence of a 20-water MNC in the mass spectra for this hydrated ion, 17,18,43,44 and results from prior IRPD spectroscopy measurements of Na + (H 2 O) 20 at cold temperatures. 7 There appears to be a slight blue-shift in the AAD peak in the spectra of Na + (H 2 O) 20 at 315 and 355 K. This may be due to the appearance of new structures for which hydrogen bonding is slightly weaker.…”

supporting

confidence: 80%

“…There are several MNCs in the distributions of Cs + (H 2 O) n at both temperatures, but Cs + (H 2 O) 20 is especially prominent at low temperature. The MNCs in the mass spectra of Cs + (H 2 O) n and Na + (H 2 O) n at 135 K have been observed previously. ,,,, …”

supporting

confidence: 63%

“…The MNCs in the mass spectra of Cs + (H 2 O) n and Na + (H 2 O) n at 135 K have been observed previously. 7,11,17,43,44 At the higher cell temperature, the ion distribution shifts to lower m/z because more extensively hydrated ions lose water molecules inside the ion cell. Several MNCs for Cs + (H 2 O) n persist at all temperatures, with Cs + (H 2 O) 20 the most abundant, consistent with a population of highly stable structures throughout this entire temperature range.…”

mentioning

confidence: 99%

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Effects of Temperature on Cs⁺(H₂O)₂₀ Clathrate Structure

Stachl

Williams

2020

J. Phys. Chem. Lett.

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Clusters consisting of 20 water molecules and a single cesium ion are especially stable due to their clathrate structure that is composed exclusively of three-coordinate water molecules. Clathrate stability was investigated using infrared photodissociation (IRPD) spectroscopy in the free-OH stretching region (∼3600–3800 cm–1) at ion cell temperatures between 135 and 355 K. At 275 K and colder, IRPD spectra of Cs+(H2O)20 have just one acceptor–acceptor–donor band. At higher temperatures, a higher-energy acceptor–donor band emerges and grows in intensity. Non-clathrate Na+(H2O)20 structures contain both of these bands, which do not change significantly in intensity over the temperature range. These results indicate a rapid onset in the conversion from clathrate to non-clathrate structures with temperature and suggest that some clathrate population remains even at the highest temperatures investigated. These results provide new insights into the role of entropy in clathrate stability.

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confidence: 80%

supporting

confidence: 63%

mentioning

confidence: 99%

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Effects of Temperature on Cs⁺(H₂O)₂₀ Clathrate Structure

Stachl

Williams

2020

J. Phys. Chem. Lett.

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“…This occurs despite the fact that only two sites are in play because the network topologies are quite diverse with respect to the H-bond configurations in the surrounding hydration shells, with the result that the bound OH (hereafter OH b ) contributions occur over hundreds of wavenumbers. Nonetheless, these overlapping contributions could be completely disentangled by leveraging cluster regime suppression of H/D isotopic exchange. , This allows the incorporation of a single, intact H 2 O molecule into an otherwise perdeuterated water cage. The labeled water was observed to statistically occupy all spectroscopically distinct sites, creating an isotopologue that is a heterogeneous ensemble of isotopomers that differ according to the site occupied by the isotopic label.…”

Section: Introductionmentioning

confidence: 99%

Isolating the Contributions of Specific Network Sites to the Diffuse Vibrational Spectrum of Interfacial Water with Isotopomer-Selective Spectroscopy of Cold Clusters

et al. 2020

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Decoding the structural information contained in the interfacial vibrational spectrum of water requires understanding how the spectral signatures of individual water molecules respond to their local hydrogen bonding environments. In this study, we isolated the contributions for the five classes of sites that differ according to the number of donor (D) and acceptor (A) hydrogen bonds that characterize each site. These patterns were measured by exploiting the unique properties of the water cluster cage structures formed in the gas phase upon hydration of a series of cations M + •(H 2 O) n (M = Li, Na, Cs, NH 4 , CH 3 NH 3 , H 3 O, and n = 5, 20−22). This selection of ions was chosen to systematically express the A, AD, AAD, ADD, and AADD hydrogen bonding motifs. The spectral signatures of each site were measured using two-color, IR−IR isotopomer-selective photofragmentation vibrational spectroscopy of the cryogenically cooled, mass selected cluster ions in which a single intact H 2 O is introduced without isotopic scrambling, an important advantage afforded by the cluster regime. The resulting patterns provide an unprecedented picture of the intrinsic line shapes and spectral complexities associated with excitation of the individual OH groups, as well as the correlation between the frequencies of the two OH groups on the same water molecule, as a function of network site. The properties of the surrounding water network that govern this frequency map are evaluated by dissecting electronic structure calculations that explore how changes in the nearby network structures, both within and beyond the first hydration shell, affect the local frequency of an OH oscillator. The qualitative trends are recovered with a simple model that correlates the OH frequency with the network-modulated local electron density in the center of the OH bond.

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“…The interaction of ions with water molecules is not only of fundamental interest for electrochemistry, electrocatalysis, and energy storage but also important for atmospheric and biological processes. , Up to now, the ion–water interaction has been studied experimentally mainly in the liquid − and gas phases − but rarely in the solid phase. − A microscopic understanding has been developed in theory by molecular dynamics simulations , and by density functional theory calculations. ,,,− …”

Section: Introductionmentioning

confidence: 99%

Structural Changes to Supported Water Nanoislands Induced by Kosmotropic Ions

et al. 2019

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We report the influence of lithium ions on binding and structure of water nanoislands on Au(111) by temperature-programmed desorption and variable-temperature scanning tunneling microscopy. Water coverages between a fraction and full bilayer and two lithium coverages (<0.15% ML) are explored. Lithium enhances selectively the binding of some of the water molecules on precovered Au(111) as compared to water on pristine Au(111), which is revealed by an increase of the water desorption temperature by approx. 10 K. Surprisingly, the effect of lithium on the structure of water is much more extended than expected from these desorption experiments. A small amount of lithium changes the structure of water nanoislands drastically compared to those on pristine Au(111). On pristine Au(111), water ice grows in the form of crystalline islands that are two or three bilayers high. On Li precovered Au(111), the islands are more corrugated, at a 5 times broader apparent height distribution and much smaller, at a 4 times smaller area distribution. These changes reflect the influence of lithium as a structure maker, or kosmotrope, on water. Our study provides unprecedented real-space information of the influence of a kosmotrope on the water structure at the nanoscale. We utilize its kosmotropic behavior to provide real-space images of desorption.

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Proton mobility and stability of water clusters containing alkali metal ions

Cited by 20 publications

References 62 publications

Effects of Temperature on Cs⁺(H₂O)₂₀ Clathrate Structure

Effects of Temperature on Cs⁺(H₂O)₂₀ Clathrate Structure

Isolating the Contributions of Specific Network Sites to the Diffuse Vibrational Spectrum of Interfacial Water with Isotopomer-Selective Spectroscopy of Cold Clusters

Structural Changes to Supported Water Nanoislands Induced by Kosmotropic Ions

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Proton mobility and stability of water clusters containing alkali metal ions

Cited by 20 publications

References 62 publications

Effects of Temperature on Cs+(H2O)20 Clathrate Structure

Effects of Temperature on Cs+(H2O)20 Clathrate Structure

Isolating the Contributions of Specific Network Sites to the Diffuse Vibrational Spectrum of Interfacial Water with Isotopomer-Selective Spectroscopy of Cold Clusters

Structural Changes to Supported Water Nanoislands Induced by Kosmotropic Ions

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Effects of Temperature on Cs⁺(H₂O)₂₀ Clathrate Structure

Effects of Temperature on Cs⁺(H₂O)₂₀ Clathrate Structure