2017
DOI: 10.1021/acs.jctc.6b01077
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Dehydrogenation Free Energy of Co2+(aq) from Density Functional Theory-Based Molecular Dynamics

Abstract: Electron and proton transfers are important steps occurring in chemical reactions. The often used approach of calculating the energy differences of those steps using methods based on geometry optimizations neglects the influence of dynamic effects. To further investigate this issue and inspired by research in water oxidation, we calculate in the present study the dehydrogenation free energy of aqueous Co, which is the free energy change associated with the first step of the water oxidation reaction mechanism o… Show more

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Cited by 10 publications
(13 citation statements)
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“…Using GGA formalism for calculating redox potentials, instead, have shown significant nonlinearity in the solvent reorganization. [41] The worse performance of the GGA formalism over hybrid functionals is associated with the misalignment of the water bands and excessive mixing of the solvent and solute electronic states, leading to a systematic underestimation of the reduction free energies. [42]…”
Section: Computational Methodologymentioning
confidence: 99%
“…Using GGA formalism for calculating redox potentials, instead, have shown significant nonlinearity in the solvent reorganization. [41] The worse performance of the GGA formalism over hybrid functionals is associated with the misalignment of the water bands and excessive mixing of the solvent and solute electronic states, leading to a systematic underestimation of the reduction free energies. [42]…”
Section: Computational Methodologymentioning
confidence: 99%
“…fixed charge force fields, polarisable force fields and hybrid quantum mechanics/molecular mechanics (QM/MM) potentials. [15][16][17] There has been some success in the application of explicit solvent models to predict organic and inorganic reaction mechanisms, [18][19][20] electrochemistry, [21][22][23][24][25][26][27] and pKa values. [28][29][30][31] However, given the size of these systems and the need for extensive configurational sampling, explicit solvent simulations are generally carried out using classical MM force fields or hybrid QM/MM potentials.…”
Section: Introductionmentioning
confidence: 99%
“…Beyond that there are more sophisticated protocols that apply AIMD to explicitly solvated systems in order to determine E red and pK A values (Cheng et al, 2009 ; Sulpizi and Sprik, 2010 ). In the context of water oxidation the dehydrogenation free energy Δ G (PCET) is of particular interest, which is also accessible by a related protocol, as has been shown by Hodel and Luber ( 2017 ).…”
Section: Choosing a Model System And An Appropriate Computational mentioning
confidence: 96%