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Solvent-mediated Isotope Effects Strongly Influence the Early Stages of Calcium Carbonate Formation : Exploring D<sub>2</sub>O vs. H<sub>2</sub>O in a Combined Computational and Experimental Approach

Solvent-mediated Isotope Effects Strongly Influence the Early Stages of Calcium Carbonate Formation : Exploring D2O vs. H2O in a Combined Computational and Experimental Approach

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KING, Michael, Jonathan Thomas AVARO, Christine PETER, Karin HAUSER, Denis GEBAUER, 2022. Solvent-mediated Isotope Effects Strongly Influence the Early Stages of Calcium Carbonate Formation : Exploring D2O vs. H2O in a Combined Computational and Experimental Approach. In: Faraday Discussions. Royal Society of Chemistry (RSC). 235, pp. 36-55. ISSN 1359-6640. eISSN 1364-5498. Available under: doi: 10.1039/D1FD00078K

@article{King2022-07-14Solve-57037, title={Solvent-mediated Isotope Effects Strongly Influence the Early Stages of Calcium Carbonate Formation : Exploring D2O vs. H2O in a Combined Computational and Experimental Approach}, year={2022}, doi={10.1039/D1FD00078K}, volume={235}, issn={1359-6640}, journal={Faraday Discussions}, pages={36--55}, author={King, Michael and Avaro, Jonathan Thomas and Peter, Christine and Hauser, Karin and Gebauer, Denis} }

Hauser, Karin Gebauer, Denis 2022-03-29T09:37:37Z In experimental studies, heavy water (D<sub>2</sub>O) is employed, e.g., so as to shift the spectroscopic solvent background, but any potential effects of this solvent exchange on reaction pathways are often neglected. While the important role of light water (H<sub>2</sub>O) during the early stages of calcium carbonate formation has been realized, studies into the actual effects of aqueous solvent exchanges are scarce. Here, we present a combined computational and experimental approach to start to fill this gap. We extended a suitable force field for molecular dynamics (MD) simulations. Experimentally, we utilised advanced titration assays and time-resolved attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. We find distinct effects in various mixtures of the two aqueous solvents, and in pure H<sub>2</sub>O or D<sub>2</sub>O. Disagreements between the computational results and experimental data regarding the stabilities of ion associates might be due to the unexplored role of HDO, or an unprobed complex phase behaviour of the solvent mixtures in the simulations. Altogether, however, our data suggest that calcium carbonate formation might proceed “more classically” in D<sub>2</sub>O. Also, there are indications for the formation of new structures in amorphous and crystalline calcium carbonates. There is huge potential towards further improving the understanding of mineralization mechanisms by studying solvent-mediated isotope effects, also beyond calcium carbonate. Last, it must be appreciated that H<sub>2</sub>O and D<sub>2</sub>O have significant, distinct effects on mineralization mechanisms, and that care has to be taken when experimental data from D<sub>2</sub>O studies are used, e.g., for the development of H<sub>2</sub>O-based computer models. Attribution-NonCommercial 3.0 Unported Avaro, Jonathan Thomas 2022-07-14 Peter, Christine eng King, Michael King, Michael Avaro, Jonathan Thomas Gebauer, Denis Hauser, Karin Solvent-mediated Isotope Effects Strongly Influence the Early Stages of Calcium Carbonate Formation : Exploring D<sub>2</sub>O vs. H<sub>2</sub>O in a Combined Computational and Experimental Approach 2022-03-29T09:37:37Z Peter, Christine

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