Search research articles

ABOUT JoVE

Overview Leadership Blog JoVE Help Center

AUTHORS

Publishing Process Editorial Board Scope & Policies Peer Review FAQ Submit

LIBRARIANS

Testimonials Subscriptions Access Resources Library Advisory Board FAQ

RESEARCH

JoVE Journal Methods Collections JoVE Encyclopedia of Experiments Archive

EDUCATION

JoVE Core JoVE Business JoVE Science Education JoVE Lab Manual Faculty Resource Center Faculty Site

Terms & Conditions of Use

Related Concept Videos

Electrostatic Boundary Conditions

Electrostatic Boundary Conditions

Consider an external electric field propagating through a homogeneous medium. When the electric field crosses the surface boundary of the medium, it undergoes a discontinuity. The electric field can be resolved into normal and tangential components. The amount by which the field changes at any boundary is given by the difference between the field components above and below the surface boundary.
The surface integral of an electric field is given by Gauss's law in integral form and is related to...

Electrostatic Boundary Conditions in Dielectrics

Electrostatic Boundary Conditions in Dielectrics

When an electric field passes from one homogeneous medium to another, crossing the boundary between the two mediums imparts a discontinuity in the electric field. This results in electrostatic boundary conditions that depend on the type of mediums the field propagates through.
Consider a case where both the mediums across a boundary are two different dielectric materials. Recall that the electric field and electric displacement are proportional and related through the material's permittivity....

Nuclear Overhauser Enhancement (NOE)

Nuclear Overhauser Enhancement (NOE)

Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling. This phenomenon, called the nuclear Overhauser enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring spin-active...

Electron Affinity

Electron Affinity

The electron affinity (EA) is the energy change for adding an electron to a gaseous atom to form an anion (negative ion).

π Electron Effects on Chemical Shift: Overview

π Electron Effects on Chemical Shift: Overview

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,...

Electronegativity

Electronegativity

Whether a bond is nonpolar or polar covalent is determined by a property of the bonding atoms called electronegativity.

You might also read

Related Articles

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

Sort by

Same author

Constrained Multipole Moment Density Functional Theory for the Frozen Contribution in Non-Covalent Complexes.

Journal of chemical theory and computation·2026

Same author

The interlocking process in molecular machines explained by a combined approach: the nudged elastic band method and machine learning potential.

Chemical science·2026

Same author

Removing Orbital-Dependence to Improve Exchange-Correlation Functional Accuracy.

The journal of physical chemistry. A·2025

Same author

Generalized quadratic model for charge transfer.

Physical chemistry chemical physics : PCCP·2025

Same author

An elementary derivation of the "|Δμ| big is good" rule and its implications in several reactivity principles.

The Journal of chemical physics·2025

Same author

Discovery of Spin-Crossover Materials with Equivariant Graph Neural Networks and Relevance-Based Classification.

Journal of chemical theory and computation·2025

Search research articles

Related Experiment Video

Updated: Dec 30, 2025

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

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

Published on: May 27, 2020

Negative Electron Affinities and Derivative Discontinuity Contribution from a Generalized Gradient Approximation

Javier Carmona-Espíndola¹, José L Gázquez², Alberto Vela³

¹Departamento de Química , CONACYT-Universidad Autónoma Metropolitana-Iztapalapa , Av. San Rafael Atlixco 186 , Ciudad de México , 09340 , México.

The Journal of Physical Chemistry. A

|January 25, 2020

Summary

New methods accurately calculate negative electron affinities using density functional theory. The nearly correct asymptotic potential (NCAP) functional and perturbation corrections improve predictions for molecular electron affinities.

More Related Videos

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

Published on: June 8, 2022

Electron Channeling Contrast Imaging for Rapid III-V Heteroepitaxial Characterization

Electron Channeling Contrast Imaging for Rapid III-V Heteroepitaxial Characterization

Published on: July 17, 2015

Related Experiment Videos

Last Updated: Dec 30, 2025

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

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

Published on: May 27, 2020

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

Thermochemical Studies of NiII and ZnII Ternary Complexes Using Ion Mobility-Mass Spectrometry

Published on: June 8, 2022

Electron Channeling Contrast Imaging for Rapid III-V Heteroepitaxial Characterization

Electron Channeling Contrast Imaging for Rapid III-V Heteroepitaxial Characterization

Published on: July 17, 2015

Area of Science:

Quantum Chemistry
Computational Materials Science
Theoretical Chemistry

Background:

Accurate calculation of electron affinities is crucial for understanding molecular properties and chemical reactivity.
Traditional density functional methods often struggle with the accurate prediction of negative electron affinities due to issues with asymptotic potential behavior.

Purpose of the Study:

To present two novel, systematic methods for calculating negative electron affinities using ground-state density functional theory.
To evaluate the accuracy and performance of these methods on a diverse set of molecules.

Main Methods:

Utilizing the lowest unoccupied molecular orbital energy shift from the nearly correct asymptotic potential (NCAP) nonempirical, constraint-based generalized gradient approximation exchange functional.
Employing a second-order perturbation calculation of the derivative discontinuity based on the NCAP exchange-correlation potential.

Main Results:

The NCAP functional provides a reasonably accurate description of negative electron affinities for thirty-eight molecules.
Further improvement in accuracy is achieved through the application of the second-order perturbation correction.

Conclusions:

The asymptotic behavior of the exchange-correlation potential significantly impacts the calculation of negative electron affinities.
The NCAP functional demonstrates versatility and effectiveness, especially when combined with perturbation corrections, for predicting negative electron affinities.