Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Concept Videos

IR Absorption Frequency: Delocalization01:04

IR Absorption Frequency: Delocalization

1.2K
Electron delocalization refers to the distribution of electrons across multiple atoms within a molecule rather than being confined to a single atom or bond. This phenomenon is common in systems with conjugated bonds—structures where alternating single and double bonds allow π-electrons to move freely across the network. The movement of electrons stabilizes the molecule and can affect various chemical properties, including vibrational frequencies observed in IR spectroscopy.
In IR...
1.2K
Photochemical Electrocyclic Reactions: Stereochemistry01:26

Photochemical Electrocyclic Reactions: Stereochemistry

2.1K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
2.1K
Deactivation Processes: Jablonski Diagram01:25

Deactivation Processes: Jablonski Diagram

1.4K
Luminescence, the emission of light by a substance that has absorbed energy, is a process that involves the interaction of molecules with light. The energy-level diagram, or Jablonski diagram, is a graphical representation of these interactions, illustrating the various states and transitions a molecule can undergo. In a typical Jablonski diagram, the lowest horizontal line represents the ground-state energy of the molecule, which is usually a singlet state. This state represents the energies...
1.4K
Regioselective Formation of Enolates01:33

Regioselective Formation of Enolates

3.2K
As depicted in the figure below, the unsymmetrical ketones can form two possible enolates:  less substituted or more substituted enolates. Usually, the thermodynamic enolates are formed from the more substituted α-carbon atom, while the kinetic enolates are formed faster by deprotonation from the less substituted position. The thermodynamic enolates have lower energy, so they are  more stable. But the energy required to form kinetic enolates is less.
3.2K
π Electron Effects on Chemical Shift: Overview01:27

π Electron Effects on Chemical Shift: Overview

1.4K
An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0,...
1.4K
Regioselectivity and Stereochemistry of Hydroboration02:36

Regioselectivity and Stereochemistry of Hydroboration

9.2K
A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
9.2K

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Kinetics and Energetics of Electron Transfer to Dimer Radical Cations.

The journal of physical chemistry. B·2023
Same author

Pushing the limits of the electrochemical window with pulse radiolysis in chloroform.

Physical chemistry chemical physics : PCCP·2020
Same author

General Method for Determining Redox Potentials without Electrolyte.

The journal of physical chemistry. A·2020
Same author

The Impact of Huge Structural Changes on Electron Transfer and Measurement of Redox Potentials: Reduction of <i>ortho</i>-12-Carborane.

The journal of physical chemistry. B·2019
Same author

Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids.

The journal of physical chemistry. B·2019
Same author

Electron Transport with Mobility, μ > 86 cm<sup>2</sup>/(V s), in a 74 nm Long Polyfluorene.

The journal of physical chemistry letters·2018

Related Experiment Video

Updated: Dec 7, 2025

Bimolecular Fluorescence Complementation
08:54

Bimolecular Fluorescence Complementation

Published on: April 15, 2011

28.4K

Inverted Region in Bimolecular Electron Transfer in Solution Enabled by Delocalization.

Norihiko Takeda1, John R Miller1

  • 1Chemistry Division, Brookhaven National Laboratory, Upton, New York 11937, United States.

Journal of the American Chemical Society
|September 29, 2020
PubMed
Summary

Electron transfer rate constants show an inverted region, explained by theory and influenced by donor size. Smaller electronic couplings in delocalized systems enable this Marcus inverted region, crucial for energy storage efficiency.

More Related Videos

Spatial Separation of Molecular Conformers and Clusters
10:37

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

11.4K
Single-Molecule F&#246;rster Resonance Energy Transfer Methods for Real-Time Investigation of the Holliday Junction Resolution by GEN1
11:27

Single-Molecule Förster Resonance Energy Transfer Methods for Real-Time Investigation of the Holliday Junction Resolution by GEN1

Published on: September 18, 2019

9.8K

Related Experiment Videos

Last Updated: Dec 7, 2025

Bimolecular Fluorescence Complementation
08:54

Bimolecular Fluorescence Complementation

Published on: April 15, 2011

28.4K
Spatial Separation of Molecular Conformers and Clusters
10:37

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

11.4K
Single-Molecule F&#246;rster Resonance Energy Transfer Methods for Real-Time Investigation of the Holliday Junction Resolution by GEN1
11:27

Single-Molecule Förster Resonance Energy Transfer Methods for Real-Time Investigation of the Holliday Junction Resolution by GEN1

Published on: September 18, 2019

9.8K

Area of Science:

  • Physical Chemistry
  • Materials Science
  • Electrochemistry

Background:

  • Electron transfer (ET) reactions are fundamental in chemistry and biology.
  • The Marcus theory describes the relationship between ET rate and driving force, including a potential inverted region.
  • Understanding factors influencing ET kinetics is key for applications like energy storage.

Purpose of the Study:

  • To investigate the influence of donor electronic delocalization on electron transfer kinetics.
  • To explore the occurrence and prominence of the Marcus inverted region in different donor systems.
  • To identify key parameters controlling electronic couplings for efficient electron transfer.

Main Methods:

  • Experimental measurement of bimolecular electron transfer rate constants.
  • Utilized radical anions of polydecylthiophene (P3DT), quaterthiophene (T4), and bithiophene (T2) as electron donors.
  • Employed electron transfer theory, incorporating a diffusion-controlled limit, to analyze rate data.

Main Results:

  • Observed rate constants that increased with driving force, plateaued, and then decreased (inverted region).
  • The inverted region was most prominent for the highly delocalized P3DT radical anions.
  • Smaller electronic couplings, associated with delocalized states, were identified as enabling the inverted behavior.

Conclusions:

  • The presence of a Marcus inverted region is directly linked to the electronic delocalization of donor states.
  • Smaller electronic couplings, potentially achieved through size-mismatch, can enhance electron transfer efficiency.
  • Findings suggest strategies for optimizing electron transfer processes in energy storage applications.