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Related Concept Videos

Potential Due to a Polarized Object01:29

Potential Due to a Polarized Object

A neutral atom consists of a positively charged nucleus surrounded by a negatively charged electron cloud. When placed in an external electric field, the external electric force pulls the electrons and nucleus apart, opposite to the intrinsic attraction between the nucleus and the electrons. The opposing forces balance each other with a slight shift between the center of masses of the nucleus and the electron cloud, resulting in a polarized atom. On the other hand, a few molecules, like water,...
Radical Reactivity: Steric Effects01:10

Radical Reactivity: Steric Effects

The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
Along with electronic factors, steric factors also account...
Standard Electrode Potentials03:02

Standard Electrode Potentials

On comparing the reactivity of silver and lead, it is observed that the two ionic species, Ag+ (aq) and Pb2+ (aq), show a difference in their redox reactivity towards copper: the silver ion undergoes spontaneous reduction, while the lead ion does not. This relative redox activity can be easily quantified in electrochemical cells by a property called cell potential. This property is commonly known as cell voltage in electrochemistry, and it is a measure of the energy which accompanies the charge...
Thermodynamics: Chemical Potential and Activity01:10

Thermodynamics: Chemical Potential and Activity

The effective concentration of a species in a solution can be expressed precisely in terms of its activity. Activity considers the effect of electrolytes present in the vicinity of the species of interest and depends on the ionic strength of the solution. The activity of a species is expressed as the product of molar concentration and the activity coefficient of the species.
The thermodynamic equilibrium constant is more accurately defined in terms of activity rather than concentration.
Electrophiles02:28

Electrophiles

This lesson explains the definition, classification, and characteristic features of an electrophile that are key features of nucleophilic substitution reactions. An analysis of their charge and orbital picture helps understand their reactivity for seeking electrons. Electrophiles can be classified into positive and neutral species. Other classes include free radicals and polar functional groups.
While a positive electrophile, like a proton, reacts due to its vacant, low-energy 1s orbital, the...
Relative Reactivity of Carboxylic Acid Derivatives01:13

Relative Reactivity of Carboxylic Acid Derivatives

Carboxylic acid derivatives such as acid halides, anhydrides, esters, and amides undergo nucleophilic acyl substitution reactions with varying degrees of reactivity.
A key factor in assessing the reactivity of the acid derivatives is the basicity of the substituent or the leaving group. The lower the basicity of the leaving group, the higher the reactivity of the derivative. The basicity of the leaving group follows this order:
Halide ions < Acyloxy ions < Alkoxy ions < Amine ions

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Potentialphilicity and potentialphobicity: Reactivity indicators for external potential changes from density

Shubin Liu1, Tonglei Li, Paul W Ayers

  • 1Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, USA. shubin@email.unc.edu

The Journal of Chemical Physics
|September 26, 2009
PubMed
Summary

New potentialphilicity and potentialphobicity indicators predict molecular reactivity and geometry changes. These concepts, analogous to electrophilicity, utilize the linear response function for predicting favorable reagent interactions.

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Area of Science:

  • Quantum Chemistry
  • Chemical Reactivity Theory

Background:

  • Electrophilicity is a key concept in chemical reactivity.
  • Predicting molecular geometry changes and reagent approach requires understanding molecular response to external potentials.

Purpose of the Study:

  • Introduce potentialphilicity and potentialphobicity as new reactivity indicators.
  • Explore the role of the linear response function in these indicators.
  • Provide tools for predicting molecular geometry and reagent interactions.

Main Methods:

  • Definition of potentialphilicity and potentialphobicity indicators.
  • Utilizing the linear response function in the theoretical framework.
  • Mathematical analysis of the response function's properties.

Main Results:

  • Potentialphilicity indicators quantify energetically favorable changes in external potential.
  • Potentialphobicity indicators identify the least favorable external potential changes.
  • The linear response function is crucial for these indicators, analogous to hardness in electrophilicity.

Conclusions:

  • Potentialphilicity and potentialphobicity offer novel insights into molecular reactivity.
  • These indicators can guide predictions of molecular geometry changes.
  • The framework provides a basis for understanding favorable and unfavorable reagent-molecule interactions.