On the variations of electronic chemical potential and chemical hardness induced by solvent effects

Meneses, Lorena; Fuentealba, Patricio; Contreras, Renato

doi:10.1016/j.cplett.2006.10.124

Cited by 26 publications

(16 citation statements)

References 20 publications

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“…The first strong decrease (46.5 % of the overall difference is due to the gas phase/nhexane change) can be linked to the actual solvation. This agrees with the findings of Meneses et al [26]. The second strong decrease of 43.0 % (going from n-hexane to the more polar dichloromethane) is due to the increasing polarity of the solvent.…”

Section: Chemical Hardnesssupporting

confidence: 91%

“…Further changes are 6.0 % going from dichloromethane to 2-propanol, 2.4 % to acetonitrile and finally 1.5 % to water. These changes, in terms of percentage (100 % being the percentage when going from gas phase to water), are constant for every radical in the database and can be traced back to the estimation for changes in g upon solvation, derived from the approximate (generalized) reaction field Born's model: [22,26,40] …”

Section: Chemical Hardnessmentioning

confidence: 99%

“…This means that for neutral systems, an enhancement of the electrophilicity is seen, controlled by changes in chemical hardness and the solvation energy, with a very small contribution from the electronic chemical potential of solvation. It also appears that l solv is dependent on the polarization charges induced in the environment within the reaction field approach, and according to that same approach, g solv is independent of those charges [22,26]. Meneses et al [26] performed calculations using the continuum approach as well as the super-molecular approach to incorporate solvent effects.…”

Section: Introductionmentioning

confidence: 97%

“…It also appears that l solv is dependent on the polarization charges induced in the environment within the reaction field approach, and according to that same approach, g solv is independent of those charges [22,26]. Meneses et al [26] performed calculations using the continuum approach as well as the super-molecular approach to incorporate solvent effects. They discovered that ''independent of the sign and magnitude of the charge, the chemical hardness always decreases upon solvation because the electrostatic potential decreases as the effective radius (solute radius plus a solvation layer) of the solute increases.''…”

Section: Introductionmentioning

confidence: 97%

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Radical electrophilicities in solvent

2012

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An electrophilicity scale for radicals in solution is reported using the electrophilicity index, an important quantity in conceptual density functional theory. Five different solvents were chosen, for which the static dielectric constant covers the entire range of nonpolar to polar solvents: n-hexane (e r = 1.8819), dichloromethane (e r = 8.9300), 2-propanol (e r = 19.2640), acetonitrile (e r = 35.6880) and water (e r = 78.3553). The calculations in solution were carried out within the polarizable continuum model through the Integral Equation Formalism (IEF-PCM) approach. For water, also conductor-like screening model (COSMO) calculations are reported. The electronic chemical potential remains almost constant when going from gas phase to solution. However, large decreases in chemical hardness can be observed, resulting in more electrophilic radicals compared to the gas phase, and even influencing the overall order of the previously established gas-phase scale. Both solvation models (COSMO and IEF-PCM) lead to essentially the same results.

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Section: Chemical Hardnesssupporting

confidence: 91%

Section: Chemical Hardnessmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 97%

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Radical electrophilicities in solvent

2012

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“…To another end, the explicit solvent model takes the specific short-range interactions into considerations by including the geometrical structures of individual solvent molecules. [31][32][33][34][35] However, it is impossible to use explicit model (with thousands of solvent molecules) to include long range interactions in full QM calculation due to tremendous computational cost. The MM is then adopted in explicit solvent model to investigate the microscopic packing configurations of solution.…”

Section: Solvent Modelsmentioning

confidence: 99%

Theoretical Modeling of Hydrogen Bonding in Macromolecular Solutions: The Combination of Quantum Mechanics and Molecular Mechanics

Jiang

2010

Series in Soft Condensed Matter

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Hydrogen bonding interaction takes an important position in solutions. The non-classic nature of hydrogen bonding requires the resourcedemanding quantum mechanical (QM) calculations. The molecular mechanics (MM) method, with much lower computational load, is applicable to the large-sized system. The combination of QM and MM is an efficient way in the treatment of solution. Taking advantage of the low-cost energy-based fragmentation QM approach (in which the macromolecule is divided into several subsystems, and QM calculation is carried out on each subsystem that is embedded in the environment of background charges of distant parts), the fragmentation-based QM/MM and polarization models have been implemented for the modeling of macromolecule in aqueous solutions, respectively. Within the framework of the fragmentation-based QM/MM hybrid model, the solute is treated by the fragmentation QM calculation while the numerous solvent molecules are described by MM. In the polarization model, the polarizability is considered by allowing the partial charges and fragment-centered dipole moments to be variables, with values coming from the energy-based fragmentation QM calculations. Applications of these two methods to the solvated long oligomers and cyclic peptides have demonstrated that the hydrogen bonding interaction affects the dynamic change in chain conformations of backbone. 237 Understanding Soft Condensed Matter via Modeling and Computation Downloaded from www.worldscientific.com by NATIONAL TAIWAN UNIVERSITY on 06/30/15. For personal use only. 238

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Can Electrophilicity Act as a Measure of the Redox Potential of First‐Row Transition Metal Ions?

Moens

Roos

Jaque

et al. 2007

Chemistry A European J

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Previous contributions concerning the computational approach to redox chemistry have made use of thermodynamic cycles and Car-Parrinello molecular dynamics simulations to obtain accurate redox potential values, whereas this article adopts a conceptual density functional theory (DFT) approach. Conceptual DFT descriptors have found widespread use in the study of thermodynamic and kinetic aspects of a variety of organic and inorganic reactions. However, redox reactions have not received much attention until now. In this contribution, we prove the usefulness of global and local electrophilicity descriptors for the prediction of the redox characteristics of first row transition metal ions (from Sc(3+) | Sc(2+) to Cu(3+) | Cu(2+)) and introduce a scaled definition of the electrophilicity based on the number of electrons an electrophile ideally accepts. This scaled electrophilicity concept acts as a good quantitative estimate of the redox potential. We also identify the first solvation sphere together with the metal ion as the primary active region during the electron uptake process, whereas the second solvation sphere functions as a non-reactive continuum region.

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On the variations of electronic chemical potential and chemical hardness induced by solvent effects

Cited by 26 publications

References 20 publications

Radical electrophilicities in solvent

Radical electrophilicities in solvent

Theoretical Modeling of Hydrogen Bonding in Macromolecular Solutions: The Combination of Quantum Mechanics and Molecular Mechanics

Can Electrophilicity Act as a Measure of the Redox Potential of First‐Row Transition Metal Ions?

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