Redox Potentials from Ab Initio Molecular Dynamics and Explicit Entropy Calculations Application to Transition Metals in Aqueous Solution
| Autor: | Miguel A. Caro, Tomi Laurila, Olga Lopez-Acevedo |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
Aqueous solution
010304 chemical physics ta114 Chemistry Solvation Thermodynamics 02 engineering and technology 021001 nanoscience & nanotechnology Electrochemistry 01 natural sciences Redox Computer Science Applications chemistry.chemical_compound Solvation shell Transition metal 0103 physical sciences Physical chemistry Molecule Physical and Theoretical Chemistry 0210 nano-technology Acetonitrile |
| Zdroj: | JOURNAL OF CHEMICAL THEORY AND COMPUTATION. 13(8):3432-3441 |
| ISSN: | 1549-9618 |
| Popis: | We present a complete methodology to consistently estimate redox potentials strictly from first-principles, without any experimental input. The methodology is based on (i) ab initio molecular dynamics (MD) simulations, (ii) all-atom explicit solvation, (iii) the two-phase thermodynamic (2PT) model, and (iv) the use of electrostatic potentials as references for the absolute electrochemical scale. We apply the approach presented to compute reduction potentials of the following redox couples: Cr2+/3+, V2+/3+, Ru(NH3)62+/3+, Sn2+/4+, Cu1+/2+, FcMeOH0/1+, and Fe2+/3+ (in aqueous solution) and Fc0/1+ (in acetonitrile). We argue that fully quantum-mechanical simulations are required to correctly model the intricate dynamical effects of the charged complexes on the surrounding solvent molecules within the solvation shell. Using the proposed methodology allows for a computationally efficient and statistically stable approach to compute free energy differences, yielding excellent agreement between our computed redo... |
| Databáze: | OpenAIRE |
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