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

Radical Chain-Growth Polymerization: Chain Branching

Radical Chain-Growth Polymerization: Chain Branching

The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...

MO Theory and Covalent Bonding

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...

π Molecular Orbitals of 1,3-Butadiene

π Molecular Orbitals of 1,3-Butadiene

Conjugated dienes have lower heats of hydrogenation than cumulated and isolated dienes, making them more stable. The enhanced stabilization of conjugated systems can be understood from their π molecular orbitals.
The simplest conjugated diene is 1,3-butadiene: a four-carbon system where each carbon is sp2-hybridized and has an unhybridized p orbital that contains an unpaired electron. According to molecular orbital theory, atomic orbitals combine to form molecular orbitals such that the number...

Polymer Classification: Architecture

Polymer Classification: Architecture

Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...

Stability of Conjugated Dienes

Stability of Conjugated Dienes

Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.

Structure of Conjugated Dienes

Structure of Conjugated Dienes

Introduction
Conjugated dienes are compounds characterized by the presence of alternating double and single bonds. In a conjugated system like 1,3-butadiene, the unhybridized 2p orbital on each carbon overlaps continuously, allowing the π electrons to be delocalized across the entire molecule. In contrast, this type of overlap does not occur in cumulated and isolated dienes, such as 2,3-pentadiene and 1,4-pentadiene, respectively. Instead, the π electrons remain localized between the double...

You might also read

Related Articles

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

Sort by

Same author

The Protein Force Field Plays a Crucial Role in Obtaining Accurate Macromolecular Ensembles of IDPs.

Journal of chemical theory and computation·2026

Same author

Characterization of kerogen nanopores using 2D NMR relaxation and MD simulations.

Magnetic resonance letters·2025

Same author

Extended molecular eigenmodes treatment of dipole-dipole NMR relaxation in real fluids.

The Journal of chemical physics·2025

Same author

Molecular-Level Insights into the NMR Relaxivity of Gadobutrol Using Quantum and Classical Molecular Simulations.

Chemical & biomedical imaging·2025

Same author

Cooperative lattice theory for CO2 adsorption in diamine-appended metal-organic framework at humid direct air capture conditions.

The Journal of chemical physics·2024

Same author

Molecular Modes Elucidate the Nuclear Magnetic Resonance Relaxation of Viscous Fluids.

The journal of physical chemistry. B·2024

Search research articles

Related Experiment Video

Updated: May 28, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Higher order classical density functional theory for branched chains and rings.

Bennett D Marshall¹, Walter G Chapman

¹Department of Chemical and Biomolecular Engineering, Rice University, Houston, Texas 77005, United States.

The Journal of Physical Chemistry. B

|November 3, 2011

Summary

This study introduces a general density functional theory for polyatomic molecules, enabling accurate predictions for complex structures like branched chains and rings using molecular graphs and thermodynamic perturbation theory.

More Related Videos

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

Published on: September 26, 2016

Preparation and In Vitro Characterization of Dendrimer-based Contrast Agents for Magnetic Resonance Imaging

Preparation and In Vitro Characterization of Dendrimer-based Contrast Agents for Magnetic Resonance Imaging

Published on: December 4, 2016

Related Experiment Videos

Last Updated: May 28, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

Published on: September 26, 2016

Preparation and In Vitro Characterization of Dendrimer-based Contrast Agents for Magnetic Resonance Imaging

Preparation and In Vitro Characterization of Dendrimer-based Contrast Agents for Magnetic Resonance Imaging

Published on: December 4, 2016

Area of Science:

Physical Chemistry
Theoretical Chemistry
Computational Chemistry

Background:

Developing accurate theoretical models for polyatomic molecules is crucial for understanding their behavior in various systems.
Existing theories may struggle with complex molecular architectures and interactions.

Purpose of the Study:

To develop a general density functional theory (DFT) for polyatomic molecules.
To extend Wertheim's thermodynamic perturbation theory (TPT) to handle complex molecular structures.
To provide a framework applicable to rigid, semiflexible, branched, and cyclic molecules.

Main Methods:

Generalizing Wertheim's thermodynamic perturbation theory by taking the complete association limit.
Introducing the concept of molecular graphs to represent molecular structures.
Developing a free energy functional and segment densities for diverse molecular architectures.
Applying the theory as a second-order perturbation theory to a specific model system.

Main Results:

A general DFT framework for polyatomic molecules was successfully developed.
The theory accommodates rigid, semiflexible, branched, and cyclic molecular structures.
The free energy functional and segment densities were derived.
The theory was demonstrated on a model system with a rigid head and flexible tail in a slit pore.

Conclusions:

The developed DFT provides a versatile tool for studying complex molecular systems.
The molecular graph approach simplifies the representation of intricate molecular structures.
The theory's applicability extends to systems with varying degrees of rigidity and flexibility.