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Related Concept Videos

Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
Radical Reactivity: Overview01:11

Radical Reactivity: Overview

Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired molecule. These three...
MO Theory and Covalent Bonding02:40

MO Theory and Covalent Bonding

The molecular orbital theory describes the distribution of electrons in molecules in a manner similar to the distribution of electrons in atomic orbitals. The region of space in which a valence electron in a molecule is likely to be found is called a molecular orbital. Mathematically, the linear combination of atomic orbitals (LCAO) generates molecular orbitals. Combinations of in-phase atomic orbital wave functions result in regions with a high probability of electron density, while...
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...
Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak carbon–halogen...
Formal Charges02:42

Formal Charges

In some cases, there are seemingly more than one valid Lewis structures for molecules and polyatomic ions. The concept of formal charges can be used to help predict the most appropriate Lewis structure when more than one reasonable structure exists.

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Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
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Modeling noncovalent radical-molecule interactions using conventional density-functional theory: beware erroneous

Erin R Johnson1, Michela Salamone, Massimo Bietti

  • 1Chemistry and Chemical Biology, School of Natural Sciences, University of California, Merced, 5200 North Lake Road, Merced, California 95343, United States.

The Journal of Physical Chemistry. A
|January 18, 2013
PubMed
Summary

Density-functional theory (DFT) can overbind radical-molecule complexes due to incorrect charge transfer. DFT methods with minimal Hartree-Fock exchange show the worst performance in predicting these charge transfer issues.

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Area of Science:

  • Computational chemistry
  • Quantum chemistry
  • Theoretical chemistry

Background:

  • Density-functional theory (DFT) is widely used for molecular modeling.
  • DFT approximations can exhibit inaccuracies, particularly in charge transfer phenomena.
  • Overbinding in radical-molecule complexes is a known issue linked to DFT limitations.

Purpose of the Study:

  • To investigate the tendency of DFT approximations to overbind radical-molecule complexes.
  • To analyze the prediction of fractional charge transfer by various DFT methods.
  • To quantify the extent of overbinding in a series of radical-molecule complexes.

Main Methods:

  • Evaluation of different DFT approximations.
  • Assessment of the prediction of fractional charge transfer.
  • Quantification of Coulombic attraction in radical-molecule complexes.
  • Analysis of the relative energy levels of molecular orbitals.

Main Results:

  • DFT approximations can lead to erroneous charge transfer in radical-molecule complexes.
  • Overbinding occurs when radical singly unoccupied molecular orbitals are too low in energy.
  • DFT methods with little or no Hartree-Fock exchange perform poorly.
  • The charge-transfer problem extends beyond conventional donor-acceptor complexes.

Conclusions:

  • The charge-transfer problem in DFT is more pervasive than previously thought.
  • Certain DFT approximations are unsuitable for accurately describing radical-molecule interactions.
  • Understanding and correcting DFT's charge transfer errors is crucial for reliable molecular modeling.