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

Bond Energies and Bond Lengths02:49

Bond Energies and Bond Lengths

25.5K
Stable molecules exist because covalent bonds hold the atoms together. The strength of a covalent bond is measured by the energy required to break it, that is, the energy necessary to separate the bonded atoms. Separating any pair of bonded atoms requires energy — the stronger a bond, the greater the energy required to break it.
25.5K
IR Spectrum Peak Broadening: Hydrogen Bonding01:23

IR Spectrum Peak Broadening: Hydrogen Bonding

1.1K
The vibrational frequency of a bond is directly proportional to its bond strength. As a result, stronger bonds vibrate at higher frequencies, while weaker bonds vibrate at lower frequencies. The stretching vibration of the strong O–H bond in alcohols and phenols (very dilute solution or gas phase) appears as a sharp peak at 3600–3650 cm−1.
However, the extent of hydrogen bonding influences the observed stretching frequency and band broadening. Intermolecular or intramolecular...
1.1K
IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration01:16

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration

1.5K
A covalently bonded heteronuclear diatomic molecule can be modeled as two vibrating masses connected by a spring. The vibrational frequency of the bond can be expressed using an equation derived from Hooke's law, which describes how the force applied to stretch or compress a spring is proportional to the displacement of the spring. In this case, the atoms behave like masses, and the bond acts like a spring.
According to Hooke's law, the vibrational frequency is directly proportional to...
1.5K
Valence Bond Theory02:45

Valence Bond Theory

32.6K
Overview of Valence Bond Theory
32.6K
Bond Dissociation Energy and Activation Energy02:13

Bond Dissociation Energy and Activation Energy

9.1K
Bond energy is the energy required to break a bond homolytically. These values are usually expressed in units of kcal/mol or kJ/mol and are referred to as bond dissociation energies when given for specific bonds or average bond energies when indicated for a given type of bond over many compounds. Firstly, the bond dissociation energy for a single bond is weaker than that of a double bond, which in turn is weaker than that of a triple bond. Secondly, hydrogen forms relatively strong bonds with...
9.1K
Valence Bond Theory and Hybridized Orbitals02:38

Valence Bond Theory and Hybridized Orbitals

19.7K
According to valence bond theory, a covalent bond results when: (1) an orbital on one atom overlaps an orbital on a second atom, and (2) the single electrons in each orbital combine to form an electron pair. The strength of a covalent bond depends on the extent of overlap of the orbitals involved. Maximum overlap is possible when the orbitals overlap on a direct line between the two nuclei.
A σ bond (single bond in a Lewis structure) is a covalent bond in which the electron density is...
19.7K

You might also read

Related Articles

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

Sort by
Same author

Local Spin Density Approximation Strongly Improved by a Better-Informed Local Scaling of Its Self-Interaction Correction.

Journal of chemical theory and computation·2026
Same author

Atom-specific vibrational analysis reveals labile bonds in linear and branched PFOA molecules.

The Journal of chemical physics·2026
Same author

Noniterative Fermi-Löwdin Orbitals for Self-Interaction Correction.

The journal of physical chemistry. A·2026
Same author

Polarizability of Polymers Using One-Electron Self-Interaction-Corrected Density Functional Methods.

The journal of physical chemistry. A·2025
Same author

Proton Transport on Graphamine: A Deep-Learning Potential Study.

The journal of physical chemistry. C, Nanomaterials and interfaces·2025
Same author

Reactive Active Learning: An Efficient Approach for Training Machine Learning Interatomic Potentials for Reacting Systems.

Journal of chemical theory and computation·2025
Same journal

Porphyrin Aggregation Revisited: From the Four-Orbital Gouterman Model to an Eight-Orbital Framework in Porphin H-Dimers.

The journal of physical chemistry. A·2026
Same journal

Unraveling the Electronic Origin of Selectivity in Ambimodal Transition States with Valence Bond Theory.

The journal of physical chemistry. A·2026
Same journal

Mechanism and Kinetics of the Initial Oxidative Ring-Opening of Corannulene Radicals under Combustion Conditions.

The journal of physical chemistry. A·2026
Same journal

High-Resolution Absorption Spectroscopy of ND<sub>3</sub> between 59,000 and 93,000 cm<sup>-1</sup>.

The journal of physical chemistry. A·2026
Same journal

Twisted-Driven Photoionization of Aligned Chiral Molecules: Signatures of Circular and Helical Dichroism.

The journal of physical chemistry. A·2026
Same journal

Modeling the Clustering of Fumaric/Maleic Acid with Water and Na<sup>+</sup>, Cl<sup>-</sup> Ions.

The journal of physical chemistry. A·2026
See all related articles

Related Experiment Video

Updated: Aug 10, 2025

The Preparation of Electrohydrodynamic Bridges from Polar Dielectric Liquids
10:03

The Preparation of Electrohydrodynamic Bridges from Polar Dielectric Liquids

Published on: September 30, 2014

26.4K

How Do Self-Interaction Errors Associated with Stretched Bonds Affect Barrier Height Predictions?

Priyanka B Shukla1, Prakash Mishra2, Tunna Baruah2,3

  • 1Department of Chemical & Petroleum Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania 15261, United States.

The Journal of Physical Chemistry. A
|February 14, 2023
PubMed
Summary
This summary is machine-generated.

Self-interaction corrections (SIC) improve chemical reaction barrier predictions by addressing errors in density functional theory. While participant orbitals are key, spectator orbitals also significantly impact barrier heights, with locally scaled SIC showing better accuracy.

More Related Videos

Accurate Determination of the Equilibrium Surface Tension Values with Area Perturbation Tests
07:57

Accurate Determination of the Equilibrium Surface Tension Values with Area Perturbation Tests

Published on: August 30, 2019

7.5K
High Precision FRET at Single-molecule Level for Biomolecule Structure Determination
11:24

High Precision FRET at Single-molecule Level for Biomolecule Structure Determination

Published on: May 13, 2017

10.8K

Related Experiment Videos

Last Updated: Aug 10, 2025

The Preparation of Electrohydrodynamic Bridges from Polar Dielectric Liquids
10:03

The Preparation of Electrohydrodynamic Bridges from Polar Dielectric Liquids

Published on: September 30, 2014

26.4K
Accurate Determination of the Equilibrium Surface Tension Values with Area Perturbation Tests
07:57

Accurate Determination of the Equilibrium Surface Tension Values with Area Perturbation Tests

Published on: August 30, 2019

7.5K
High Precision FRET at Single-molecule Level for Biomolecule Structure Determination
11:24

High Precision FRET at Single-molecule Level for Biomolecule Structure Determination

Published on: May 13, 2017

10.8K

Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Theoretical Chemistry

Background:

  • Density functional theory (DFT) approximations often underestimate chemical reaction barrier heights due to self-interaction errors (SIEs).
  • These SIEs are linked to the overstabilization of delocalized electron densities in transition states with stretched bonds.
  • Self-interaction correction (SIC) methods, such as Perdew-Zunger (PZSIC) and locally scaled (LSIC), aim to mitigate these errors.

Purpose of the Study:

  • To analyze the contribution of individual orbitals to self-interaction correction (SIC) in chemical reaction barriers.
  • To test the hypothesis that SIC contributions primarily arise from participant orbitals (POs) involved in bond changes.
  • To compare the accuracy of PZSIC and LSIC methods in correcting barrier height underestimations.

Main Methods:

  • Utilized Fermi-Löwdin orbitals (FLOs) to perform orbital-by-orbital self-interaction correction (SIC).
  • Analyzed the contributions of participant orbitals (POs) versus spectator orbitals (SOs) to the total SIC correction.
  • Evaluated the performance of PZSIC and LSIC on the BH76 benchmark set of chemical reactions.

Main Results:

  • Stretched-bond orbitals (participant orbitals) contribute significantly to SIC, increasing barrier heights compared to LSDA.
  • The hypothesis that only participant orbitals dominate SIC contributions to barriers was not universally true; spectator orbitals can be significant.
  • A large SIC correction correlates with large LSDA errors, indicating PZSIC provides larger corrections where needed most.
  • LSIC demonstrated superior accuracy over PZSIC, particularly for reactions with small LSDA errors, due to improved reaction energy descriptions.

Conclusions:

  • While participant orbitals are crucial, spectator orbital contributions to SIC cannot be ignored for accurate barrier height predictions.
  • The magnitude of the SIC contribution serves as an indicator of the underlying LSDA error.
  • Locally scaled self-interaction correction (LSIC) offers improved accuracy over PZSIC for chemical reaction barrier heights.