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First-principles calculations on the micro-solvation of 3d-transition metal ions: solvation versus splitting water

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Abstract

Molecular level understanding of 3d-transition metal interaction with water molecules in various electronic states is of fundamental significance in chemistry and biology. This study systematically presents the propensity of 3d-transition metals in their variable electronic and spin states towards solvation and splitting water molecules. The topological analysis affirmed that neutral and mono-cationic complexes are prone to be partially covalent in nature from moving low to high spin states; however, coordinate bonding is observed in di- and tri-cationic ion–water complexes. Potential energy surface analysis showed a profound influence of electronic states of 3d-transition metals on the relative feasibility of bond scission and solvation competing pathways. The early neutral, high spin mono-cationic, and di-cationic transition metals prefer solvation over splitting the water molecule. Similarly, mid- and late-transition metal ions in the first two electronic states, irrespective of the spin state, show higher preferences towards solvation. In contrast, neutral and tri-cationic ions tend to form either insertion complexes, hydroxides, or hydrides over the ion–water complexes, suggesting a preference to split the water molecule. Thus, tuning the electronic and micro-environment will help in the design of transition metals catalysts for water splitting.

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Acknowledgements

DST is thanked for the J. C. Bose National Fellowship by GNS. For the INSPIRE fellowship, YBK thanks DST, and for the institutional fellowship, NK thanks CSIR-NEIST. We are also grateful to DBT to provide funding in the form of the Centre of Excellence for ACDSD.

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  1. Academy of Scientific and Innovative Research (AcSIR), Ghaziabad, Uttar Pradesh, 201002, India

    Y. Bhargav Kumar & G. Narahari Sastry

  2. Advanced Computation and Data Sciences Division, CSIR-North East Institute of Science and Technology, Jorhat, Assam, India

    Y. Bhargav Kumar, Nandan Kumar & G. Narahari Sastry

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GNS has conceived the idea and guided the study. YBK and NK performed the calculations. YBK, and NK performed the data analysis and made the tables and figures for the manuscript and provided the draft of the manuscript. The final draft was read and finalized by all authors.

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Bhargav Kumar, Y., Kumar, N. & Narahari Sastry, G. First-principles calculations on the micro-solvation of 3d-transition metal ions: solvation versus splitting water. Theor Chem Acc 142, 35 (2023). https://doi.org/10.1007/s00214-023-02974-1

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