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WIREs Comput Mol Sci
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Hybrid discrete‐continuum solvation methods

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Abstract Hybrid discrete‐continuum approaches for solvation have been widely applied for diverse problems in chemistry suck as pKa calculation in aqueous and nonaqueous solvents, activation free energy barriers for ionic processes in solution, and surface reactions. A special version of this approach, the cluster‐continuum quasichemical model, has also been used for establishing a single‐ion solvation free energy scale in different solvents compatible with the tetraphenylarsonium tetraphenylborate assumption. The use of discrete‐continuum solvation methods can lead to meaningful improvement with respect to pure continuum solvation models for modeling diverse chemical process in solution. In the case of pKa calculations, there are cases where the root mean squared error is as large as 7 pKa units with pure continuum solvation model and becomes around 1 pKa unit with the hybrid approach. For complex reactions in solution, errors as large as 10 kcal/mol for activation free energies with the pure continuum approach can be substantially reduced with the inclusion of explicit solvent molecules. A discussion of the theory of hybrid discrete‐continuum methods is also presented and further development is expected in the coming years. This article is categorized under: Structure and Mechanism > Reaction Mechanisms and Catalysis Software > Quantum Chemistry Molecular and Statistical Mechanics > Free Energy Methods
Solvation of the methoxide ion in water solution using different approaches
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Theoretical versus experimental pH‐rate profile for the oxidation of dimethyl sulfide by hydrogen peroxide using pure continuum and cluster‐continuum methods. (Reproduced from Reference Copyright 2014 John Wiley & Sons)
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Proposed mechanism for the acid‐catalyzed hydrolysis of a typical amide such as formamide
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Transition state for OH(H2O)3 addition to HCOOCH3
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The calculated activation free energy, ΔG#, for the different pathways of the OH/HCOOMe reaction in aqueous solution. (Values from Reference )
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A plot of pKa(exp) as a function of pKa calculated using the cluster‐continuum approach of Pliego and Riveros
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Thermodynamic cycle used to calculate the pKa of acid HA from reaction (29), using OH as the reference species (Ref)
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Variation of the solvation free energy of the Li+ ion in methanol solution with the number of explicit methanol molecules calculated by the cluster‐continuum (open circles) and quasichemical theory (filled circles) approach. Continuum contribution calculated by the PCM method. In the primitive quasichemical approach, the sum goes up to the number of explicit methanol (Equation (12)). (Data from Reference )
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Molecular and Statistical Mechanics > Free Energy Methods
Software > Quantum Chemistry
Structure and Mechanism > Reaction Mechanisms and Catalysis

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