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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired molecule. These three...
Equation of Rotational Dynamics01:08

Equation of Rotational Dynamics

Angular variables are introduced in rotational dynamics. Comparing the definitions of angular variables with the definitions of linear kinematic variables, it is seen that there is a mapping of the linear variables to the rotational ones. Linear displacement, velocity, and acceleration have their equivalents in rotational motion, which are angular displacement, angular velocity, and angular acceleration. Similar to the rotational variables, a mapping exists from Newton's second law of motion...
Radicals: Electronic Structure and Geometry01:07

Radicals: Electronic Structure and Geometry

This lesson delves into the geometry of a radical, which is influenced by the electronic structure of the molecule. The principle is similar to that of a lone pair, where the unpaired electron influences the geometry at the radical center.
Accordingly, the structure of a trivalent radical lies between the geometries of carbocations and carbanions. An sp2-hybridized carbocation is trigonal planar, while an sp3-hybridized carbanion is trigonal pyramidal. Here, the difference in geometry is...
Radical Chain-Growth Polymerization: Mechanism01:09

Radical Chain-Growth Polymerization: Mechanism

The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into the...
Thermal Sigmatropic Reactions: Overview01:16

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Methods for Measuring the Orientation and Rotation Rate of 3D-printed Particles in Turbulence
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Pseudorotation-driven dynamical structure of the tropyl radical.

Hai-Bo Yi1, Han Myoung Lee, Seung Bum Suh

  • 1Center for Superfunctional Materials, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang 790-784, Korea.

The Journal of Chemical Physics
|November 10, 2006
PubMed
Summary

The tropyl radical

Area of Science:

  • Quantum Chemistry
  • Chemical Physics
  • Spectroscopy

Background:

  • The neutral tropyl radical's structure, energetics, and vibrational modes remain unclear despite extensive research.
  • A key vibrational mode's frequency varies dramatically with computational methods, posing a long-standing puzzle.

Purpose of the Study:

  • To elucidate the origin of the tropyl radical's peculiar vibrational mode.
  • To clarify the interconversion mechanism between its Jahn-Teller configurations.

Main Methods:

  • Computational analysis of the tropyl radical's potential energy surface.
  • Investigation of pseudorotation pathways and symmetry considerations.

Main Results:

  • The peculiar vibrational mode arises from pseudorotation between two nearly isoenergetic Jahn-Teller configurations (2B1 and 2A2).

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  • Interconversion occurs via a Cs symmetry pathway, not D7h or C2v, with a negligible barrier.
  • The tropyl radical exhibits a dynamically identical structure with partial quantum distributions.

    • Conclusions:

    • The tropyl radical's effective D7h structure emerges from dynamical transitions between 2B1 and 2A2 configurations via multiple pseudorotation pathways.
    • This explains high-temperature electron spin resonance experimental observations.