Benchmarking the Conductor-like Polarizable Continuum Model (CPCM) for Aqueous Solvation Free Energies of Neutral and Ionic Organic Molecules

Takano, Yu; Houk, K. N.

doi:10.1021/ct049977a

Cited by 1,046 publications

(855 citation statements)

References 64 publications

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“…The relative energy difference is calculated to be 0.6 kcal/mol very close to the 0.7 kcal/mol obtained using CPCM single point calculations. 22,36 Structures TS9 are similar to the most stable closed transition states located for the alkylation reaction of pyrrole with (E)-crotonaldehyde organocatalyzed by dimethylamine. 16 However, transition vector motion along the reaction coordinate of TS9 corresponds to a concerted asynchronous Diels-Alder cycloaddition reaction.…”

Section: Resultsmentioning

confidence: 87%

“…Solvation energies of a representative group of neutral, anionic, and cationic molecules, are computed relatively well with this methodology. 22 …”

Section: Methodsmentioning

confidence: 99%

“…12 The energies of all the transition structures in water with the CPCM solvation model at the HF/6-31G(d)//B3LYP/6-31G(d) level of theory and, with the UAKS cavity model have been also computed (see computational methods section). 22 Solvation energies increase both endo selectivity and enantioselectivity. For catalyst 1, an almost 100% endo selectivity was predicted, and in the case of amine 5 a 35:1 endo:exo ratio was calculated, versus the 25:1 experimental product ratio.…”

Section: Imidazolidinone Catalyzed Diels-alder Cycloadditionsmentioning

confidence: 99%

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Origins of Stereoselectivity in Diels−Alder Cycloadditions Catalyzed by Chiral Imidazolidinones

2006

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B3LYP/6-31G(d) density functional theory has been used to study Diels-Alder reactions of cyclopentadiene with α,β-unsaturated aldehydes and ketones organocatalyzed by MacMillan's chiral imidazolidinones. Preferred conformations of transition structures and reaction intermediates have been located. The dramatically different reactivities and enantioselectivities exhibited by two similar chiral imidazolidinones are rationalized.

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Section: Resultsmentioning

confidence: 87%

“…Solvation energies of a representative group of neutral, anionic, and cationic molecules, are computed relatively well with this methodology. 22 …”

Section: Methodsmentioning

confidence: 99%

Section: Imidazolidinone Catalyzed Diels-alder Cycloadditionsmentioning

confidence: 99%

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Origins of Stereoselectivity in Diels−Alder Cycloadditions Catalyzed by Chiral Imidazolidinones

2006

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“…Recently, Takano et al have performed benchmarking studies for the solute-cavity descriptions within the CPCM solvation model for the prediction of acidity constants. They found that the UAKS cavity definition, which uses united atom radii optimized at the PBE1PBE/6-31G(d) level of theory, estimates the solvation free energies within ~10.5 kJ/mol of experimental solvation free energies [76].…”

Section: Solvationmentioning

confidence: 99%

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Arumugam

Becker

2014

Minerals

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Abstract:Applications of redox processes range over a number of scientific fields. This review article summarizes the theory behind the calculation of redox potentials in solution for species such as organic compounds, inorganic complexes, actinides, battery materials, and mineral surface-bound-species. Different computational approaches to predict and determine redox potentials of electron transitions are discussed along with their respective pros and cons for the prediction of redox potentials. Subsequently, recommendations are made for certain necessary computational settings required for accurate calculation of redox potentials. This article reviews the importance of computational parameters, such as basis sets, density functional theory (DFT) functionals, and relativistic approaches and the role that physicochemical processes play on the shift of redox potentials, such as hydration or spin orbit coupling, and will aid in finding suitable combinations of approaches for different chemical and geochemical applications. Identifying cost-effective and credible computational approaches is essential to benchmark redox potential calculations against experiments. Once a good theoretical approach is found to model the chemistry and thermodynamics of the redox and electron transfer process, this knowledge can be incorporated into models of more complex reaction mechanisms that include diffusion in the solute, surface diffusion, and dehydration, to name a few. This knowledge is important to fully understand the nature of redox processes be it a geochemical process that dictates natural redox reactions or one that is being used for the optimization of a chemical process in industry. In addition, it will help identify materials that will be useful to design catalytic OPEN ACCESSMinerals 2014, 4 346 redox agents, to come up with materials to be used for batteries and photovoltaic processes, and to identify new and improved remediation strategies in environmental engineering, for example the reduction of actinides and their subsequent immobilization. Highly under-investigated is the role of redox-active semiconducting mineral surfaces as catalysts for promoting natural redox processes. Such knowledge is crucial to derive process-oriented mechanisms, kinetics, and rate laws for inorganic and organic redox processes in nature. In addition, molecular-level details still need to be explored and understood to plan for safer disposal of hazardous materials. In light of this, we include new research on the effect of iron-sulfide mineral surfaces, such as pyrite and mackinawite, on the redox chemistry of actinyl aqua complexes in aqueous solution.

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“…Takano and Houk have previously shown 28 that HF-CPCM calculations with cavities determined with use of UAKS radii produce reliable results for the aqueous free energy corrections. Moreover, they observed that CPCM is faster when large molecules are involved, and more accurate than PCM.…”

Section: Calculation Of Oxygen Atom Transfer Free Energies In Aqueousmentioning

confidence: 99%

Oxygen Atom Transfer Energetics: Assessment of the Effect of Method and Solvent

et al. 2006

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Several density functional methods, the semiempirical methods AM1 and PM3, Hartree-Fock, and Gaussian3 theories were applied to compute the oxygen atom transfer enthalpies for 14 X/XO couples (inorganic and organic systems, charged and neutral species, light and heavy main group element containing molecules). The calculated reaction enthalpies were compared to available experimental data. The G3 method alone was found to perform within the experimental error, while the popular B3LYP and BLYP functionals provided inadequate results. Solvent effects were estimated for 19 neutral and anionic X/XO couples by using the conductor-like polarizable continuum model and several cavity models coupled with the B3LYP/6-31++G-(2d,2p) level of theory. Surprisingly, the magnitude of the aqueous solvent correction was found to vary significantly for different solute cavity models, occasionally giving larger errors than the gas-phase calculation.

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Benchmarking the Conductor-like Polarizable Continuum Model (CPCM) for Aqueous Solvation Free Energies of Neutral and Ionic Organic Molecules

Cited by 1,046 publications

References 64 publications

Origins of Stereoselectivity in Diels−Alder Cycloadditions Catalyzed by Chiral Imidazolidinones

Origins of Stereoselectivity in Diels−Alder Cycloadditions Catalyzed by Chiral Imidazolidinones

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Oxygen Atom Transfer Energetics: Assessment of the Effect of Method and Solvent

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