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

729
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...
729
The Uncertainty Principle04:08

The Uncertainty Principle

23.1K
Werner Heisenberg considered the limits of how accurately one can measure properties of an electron or other microscopic particles. He determined that there is a fundamental limit to how accurately one can measure both a particle’s position and its momentum simultaneously. The more accurate the measurement of the momentum of a particle is known, the less accurate the position at that time is known and vice versa. This is what is now called the Heisenberg uncertainty principle. He...
23.1K
Hybridization of Atomic Orbitals II03:35

Hybridization of Atomic Orbitals II

31.8K
sp3d and sp3d 2 Hybridization
31.8K
Propagation of Uncertainty from Systematic Error01:10

Propagation of Uncertainty from Systematic Error

482
The atomic mass of an element varies due to the relative ratio of its isotopes. A sample's relative proportion of oxygen isotopes influences its average atomic mass. For instance, if we were to measure the atomic mass of oxygen from a sample, the mass would be a weighted average of the isotopic masses of oxygen in that sample. Since a single sample is not likely to perfectly reflect the true atomic mass of oxygen for all the molecules of oxygen on Earth, the mass we obtain from this...
482
Hybridization of Atomic Orbitals I03:24

Hybridization of Atomic Orbitals I

46.5K
The mathematical expression known as the wave function, ψ, contains information about each orbital and the wavelike properties of electrons in an isolated atom. When atoms are bound together in a molecule, the wave functions combine to produce new mathematical descriptions that have different shapes. This process of combining the wave functions for atomic orbitals is called hybridization and is mathematically accomplished by the linear combination of atomic orbitals. The new orbitals that...
46.5K
Crystal Field Theory - Octahedral Complexes02:58

Crystal Field Theory - Octahedral Complexes

26.2K
Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
26.2K

You might also read

Related Articles

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

Sort by
Same author

Benchmark assessment of collinear, mixed-reference, and spin-adapted variants of spin-flip time-dependent density functional theory, for closed- and open-shell molecules.

The Journal of chemical physics·2026
Same author

Energy-Screened Many-Body Expansion for Protein-Ligand Interactions: Examining Convergence for Metalloenzymes Through Seven-Body Interactions.

Journal of chemical theory and computation·2026
Same author

Extended Configuration-Interaction Singles Method with Core/Valence Separation (XCIS-CVS): Core-Level Spectra of Open-Shell Molecules.

Journal of chemical theory and computation·2025
Same author

Computing L- and M-edge spectra using the DFT/CIS method with spin-orbit coupling.

Physical chemistry chemical physics : PCCP·2025
Same author

Revisiting the Half-and-Half Functional.

The journal of physical chemistry. A·2025
Same author

Untangling Sources of Error in the Density-Functional Many-Body Expansion.

The journal of physical chemistry letters·2025
Same journal

Recent progress in catalytic asymmetric synthesis of triarylmethanes.

Chemical science·2026
Same journal

GFP chromophore photophysics: ultrafast dynamics and hot ground state cooling in the neutral form.

Chemical science·2026
Same journal

Large Stokes shift fluorophores from <i>meta</i>-substituted zwitterions.

Chemical science·2026
Same journal

<i>In situ</i> glycosylation-directed H-aggregation of Type I photosensitizers for synergistic biofilm eradication and promoting diabetic wound healing.

Chemical science·2026
Same journal

Substituent engineering of dynamic covalent bonds enables simultaneous enhancement of performance and recyclability.

Chemical science·2026
Same journal

Visible-light-enabled three-component carboamidation of alkenes with aryl thianthrenium salts.

Chemical science·2026
See all related articles

Related Experiment Video

Updated: Jun 7, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
08:04

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

Published on: May 27, 2020

8.4K

Delocalization error poisons the density-functional many-body expansion.

Dustin R Broderick1, John M Herbert1

  • 1Department of Chemistry & Biochemistry, The Ohio State University 151 W. Woodruff Ave. Columbus Ohio 43210 USA herbert@chemistry.ohio-state.edu.

Chemical Science
|November 21, 2024
PubMed
Summary
This summary is machine-generated.

The many-body expansion combined with density functional theory shows significant errors in ion-water interactions due to self-interaction errors. Energy-based screening can mitigate these issues, but caution is advised for this quantum chemistry method.

More Related Videos

Spatial Separation of Molecular Conformers and Clusters
10:37

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

8.9K
Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
12:11

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

8.1K

Related Experiment Videos

Last Updated: Jun 7, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
08:04

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

Published on: May 27, 2020

8.4K
Spatial Separation of Molecular Conformers and Clusters
10:37

Spatial Separation of Molecular Conformers and Clusters

Published on: January 9, 2014

8.9K
Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
12:11

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

8.1K

Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Physical Chemistry

Background:

  • The many-body expansion (MBE) is a fragment-based method for large-scale quantum chemistry calculations.
  • MBE is increasingly used for fitting force fields and in machine learning, particularly for water and aqueous systems.
  • Previous studies have not highlighted significant issues with MBE in these contexts.

Purpose of the Study:

  • To investigate the accuracy and limitations of the many-body expansion when combined with semilocal density functional theory for ion-water interactions.
  • To identify the source of errors and explore potential mitigation strategies.

Main Methods:

  • Utilized the many-body expansion approach with semilocal density functional theory (DFT).
  • Examined ion-water interactions, specifically F-(H2O)N clusters with N >= 15.
  • Tested various mitigation strategies including hybrid functionals, counterpoise correction, density correction, and dielectric continuum models.
  • Investigated energy-based screening as a potential solution.

Main Results:

  • Semilocal DFT combined with MBE exhibits wild oscillations and error accumulation in ion-water interactions for clusters N >= 15.
  • Self-interaction error in DFT is identified as the primary cause of these divergent behaviors.
  • The errors are minor in small clusters but become catastrophic in larger ones.
  • Hybrid functionals with >50% exact exchange can counteract errors, but modern meta-GGAs (ωB97X-V, SCAN, SCAN0) are insufficient.
  • Counterpoise correction, density correction, and continuum models show limited effectiveness.
  • Energy-based screening successfully prevents divergent behavior.

Conclusions:

  • Extreme caution is necessary when using the many-body expansion with density functional theory for ion-water systems.
  • Self-interaction error is a critical issue that can lead to catastrophic failures in MBE-DFT calculations.
  • Energy-based screening offers a viable strategy to improve the reliability of MBE-DFT for such systems.