Electron structure and reactivity of organofluorine compounds. 4. AMI calculations of anion radicals of primary, secondary, and tertiary perfluoroalkyl chlorides, bromides, and iodides

Rempel, G. D.; Borisov, Yu. А.; Raevskii, N. I.; Igumnov, S. M.; Rozhkov, I. N.

doi:10.1007/bf00961689

Cited by 3 publications

(2 citation statements)

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“…One electron attachment to the CF 3 X (X = Cl, Br, I) molecules are very important reactions, which were explored in many experimental − and theoretical works. − In our very recent theoretical studies, we studied in detail the most important properties of substrates and products of the one electron reduction of CF 3 X (X = Cl, Br, I) molecules in vacuo. According to this work, and also in agreement with some earlier studies, these processes proceed via formation of the locally stabilized radical anions CF 3 X¯, which further dissociate to the radical CF 3 • and halide anions X¯.…”

Section: Introductionmentioning

confidence: 99%

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Ignaczak

2012

J. Phys. Chem. A

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In this article, an effect of solvent on potential energy surfaces, constructed at the PBE1PBE/aug-cc-pVTZ level vs C-X distances for the neutral molecules CF(3)X (X = Cl, Br, I) and the corresponding radical anions CF(3)X¯, is studied using the polarizable continuum model (PCM). The properties and energy changes in these compounds in the presence of argon, acetonitrile (ACN), and dimethyl sulfoxide (DMSO) are compared to the results obtained earlier in vacuo. The presence of solvent very weakly influences the neutral molecules, but it significantly changes properties of radical anions, such as structural parameters and partial charges on atoms. The effect of solvent is manifested also in strong modification of the potential energy surfaces, on which the minima corresponding to the locally stabilized forms of CF(3)X¯ are shallower in argon, and in ACN and DMSO, they almost disappear. This in turn results in much higher energy barriers (by about 0.2-0.3 eV) for the reductive cleavage of C-X bonds in polar solvents than in vacuo. Despite different dielectric constants of ACN and DMSO, the potential energy surfaces obtained in these two solvents are very similar, and the activation energies equal, respectively, 0.635 and 0.637 eV for CF(3)Cl; 0.479 and 0.481 eV for CF(3)Br; and 0.336 and 0.337 eV for CF(3)I.

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Section: Introductionmentioning

confidence: 99%

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Ignaczak

2012

J. Phys. Chem. A

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“…The essential step in such reactions is the transfer of an electron from the electrode to the neutral CF 3 X (X = Cl,Br,I) molecules, which in solutions occurs with the simultaneous rupture of the C–X bond and formation of the radical CF 3 and anion X¯. Theoretical investigations of these processes are mostly focused on selected properties of substrates and products in the gas-phase; ,− very few take into account the solvent effect. ,, For the analysis of the reaction mechanism the most important works are those providing potential energy profiles (PES) of the neutral molecules and anions with respect to the C–X bond dissociation. In the article of Bertran et al the PES obtained at the MP2/4-31G* level for the CF 3 Cl and CF 3 Cl¯ molecules in the gas phase and in the polar solvent, introduced via the polarizable continuum model (PCM) with dielectric constant ε = 37, were presented.…”

Section: Introductionmentioning

confidence: 99%

Simulations of Adiabatic Electrochemical Reduction of the CF₃I Molecule—Assessment of Different Models

Ignaczak

2013

J. Chem. Theory Comput.

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The kinetics and mechanism of electrochemical reduction of the CF3I molecule are studied using molecular dynamics simulations. The potential energy surface used in the simulations is based on the Newns-Anderson-Schmickler Hamiltonian and on the analytical potentials fitted to points obtained from quantum calculations for the CF3I neutral molecule and anion. Two different sets of points were used for fitting: the first obtained in vacuo1 and the second in dimethyl sulfoxide,2 which yields two models, named respectively "VAC" and "SOLV." Additionally, each model was tested with two different values of the solvent reorganization energies: λ = 0.624 eV and λ = 1 eV. The results show that both models provide results which are qualitatively similar but differ quantitatively, mainly due to a shift in the overpotential η. The electron transfer coefficient is found to vary linearly at a certain range of overpotentials, but this relation changes for larger η, where it takes a parabolic-like form. The transfer coefficient is very sensitive to the λ value: at T = 298 K and η = 0.9 V, we report values α = 0.204 obtained for λ = 0.624 eV and α = 0.28 for λ = 1 eV.

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DFT study on the one-electron reduction of CF3X (X=Cl, Br, I) molecules

Ignaczak

Łaszczych

2011

Computational and Theoretical Chemistry

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Electron structure and reactivity of organofluorine compounds. 4. AMI calculations of anion radicals of primary, secondary, and tertiary perfluoroalkyl chlorides, bromides, and iodides

Cited by 3 publications

References 7 publications

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Simulations of Adiabatic Electrochemical Reduction of the CF₃I Molecule—Assessment of Different Models

DFT study on the one-electron reduction of CF3X (X=Cl, Br, I) molecules

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Electron structure and reactivity of organofluorine compounds. 4. AMI calculations of anion radicals of primary, secondary, and tertiary perfluoroalkyl chlorides, bromides, and iodides

Cited by 3 publications

References 7 publications

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF3X (X = Cl, Br, I) Molecules: A DFT PCM Study

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF3X (X = Cl, Br, I) Molecules: A DFT PCM Study

Simulations of Adiabatic Electrochemical Reduction of the CF3I Molecule—Assessment of Different Models

DFT study on the one-electron reduction of CF3X (X=Cl, Br, I) molecules

Contact Info

Product

Resources

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Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Solvent Effect on the Potential Energy Surfaces for the One-Electron Reduction of CF₃X (X = Cl, Br, I) Molecules: A DFT PCM Study

Simulations of Adiabatic Electrochemical Reduction of the CF₃I Molecule—Assessment of Different Models