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Photoelectron Imaging of Anions Illustrated by 310 Nm Detachment of F−

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Published on: July 27, 2018

The Perfluoro Cage Effect: A Search for Electron-Encapsulating Molecules.

Abhik Ghosh¹, Jeanet Conradie^1,2

¹Department of Chemistry, UiT - The Arctic University of Norway, Tromsø N-9037, Norway.

|February 13, 2023

Summary

Researchers explored the perfluoro cage effect (PCE) in perfluorinated organic molecules. DFT calculations revealed several new cage molecules capable of encapsulating electrons, with larger cages showing higher electron affinities.

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Area of Science:

Quantum chemistry
Organic chemistry
Materials science

Background:

Perfluorinated polyhedral organic molecules were predicted to encapsulate electrons.
This behavior, the perfluoro cage effect (PCE), was recently confirmed for perfluorocubane.

Purpose of the Study:

To identify additional perfluorinated cage molecules exhibiting the PCE.
To investigate the relationship between molecular size and electron affinity.

Main Methods:

Density Functional Theory (DFT) calculations.
Utilized well-tested exchange-correlation functionals and large STO-QZ4P basis sets.

Main Results:

Identified several perfluorinated cages, including [n]prismanes, [n]asteranes, twistane, and norbornadiene dimers, exhibiting the PCE.
Observed electron affinities ranging from under 1 eV to over 2 eV.
A size effect was noted, with larger cages showing higher electron affinities, exceeding 3 eV for perfluorinated dodecahedrane and C60.

Conclusions:

Several new perfluorinated cage molecules demonstrate the perfluoro cage effect.
Molecular size significantly influences electron affinity in these systems.
The PCE is less pronounced in smaller perfluorinated cages like tetrahedrane.