Carbonate and carbonate anion radicals in aqueous solutions exist as CO3(H2O)62− and CO3(H2O)6˙− respectively: the crucial role of the inner hydration sphere of anions in explaining their properties

Literature Information

Publication Date 2018-03-06
DOI 10.1039/C7CP08240A
Impact Factor 3.676
Authors

Shmuel Zilberg, Amir Mizrahi, Haya Kornweitz


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Abstract

An effort to reproduce the chemical and physical properties of carbonate and carbonate anion radicals in aqueous solutions by DFT proves that one has to include an inner hydration sphere of six water molecules for both anions. Application of the SMD model to CO3(H2O)62− and CO3(H2O)6˙− enables achievement of the experimental value of the redox potential of the CO3(H2O)6˙−/2− couple. This is a result of the direct inclusion of a considerable charge transfer (CT) from CO32− to its inner hydration sphere in the calculation of the hydration effect. The HOMO of clusters is an analogue of the non-bonding σ-type a2′-HOMO of the parent CO3 moiety with a σ*(OH) contribution. This is a MO manifestation of the CT to the first hydration shell. The localization of the CT on the first hydration shell also re-produces the very strong OH⋯O stretch peak. Furthermore, the very large difference in the hydration energies of CO32− and CO3˙− which causes the very large differences in the length of the C–O⋯H–O hydrogen bonds suggests that the oxidations by CO3˙− proceed via the inner sphere mechanism.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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