The effect of halide and iodate anions on the hydrogen-bonding network of water in aqueous nanodrops

Literature Information

Publication Date 2016-08-17
DOI 10.1039/C6CP05033F
Impact Factor 3.676
Authors

Satrajit Chakrabarty, Evan R. Williams


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Abstract

The hydration of halide and iodate anions was investigated using electrospray ionization (ESI) mass spectrometry and infrared photodissociation (IRPD) spectroscopy. The average cluster sizes, determined from the abundances of X−(H2O)n (X− = F−, Cl−, Br−, I−, IO3−) in the ESI mass spectra, follow the order F− > IO3− ≈ Cl− > Br− > I−. The average cluster sizes and solution hydration enthalpies of the halides increase linearly with decreasing ionic radii, but IO3− does not fit this trend. The correlation between average cluster sizes and solution hydration enthalpies indicates that there is a similar relationship between ion–water interactions in these large gas-phase clusters and in bulk solution. The abundances of odd number clusters between n = 49 and 55 for I−, Br− and Cl− are enhanced but those for F− and IO3− are not. I− and IO3− have nearly the same ionic radii, but evidence suggests that these ions interact with water molecules differently both in solution and in small clusters. IRPD spectra of I−(H2O)n and IO3−(H2O)n, measured for select cluster sizes between n = 30 and 75 reveal differences in the hydrogen-bonding network of water molecules in these two ions even for sizes around n = 50. This indicates that differences in hydration motifs reported previously for the first hydration shells of I− and IO3− propagate to water molecules past the second solvation shell, a phenomenon that has not been reported previously for singly charged anions.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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