Jump to main content
Jump to site search

Issue 9, 2021
Previous Article Next Article

Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields

Author affiliations

Abstract

While the influence of intramolecular electric fields is a known feature in enzymes, the use of oriented external electric fields (EEF) to enhance or inhibit molecular reactivity is a promising topic still in its infancy. Herein we will explore computationally the effects that EEF can provoke in simple molecules close to the absolute zero, where quantum tunnelling (QT) is the sole mechanistic option. We studied three exemplary systems, each one with different reactivity features and known QT kinetics: π bond-shifting in pentalene, Cope rearrangement in semibullvalene, and cycloreversion of diazabicyclohexadiene. The kinetics of these cases depend both on the field strength and its direction, usually giving subtle but remarkable changes. However, for the cycloreversion, which suffers large changes on the dipole through the reaction, we also observed striking results. Between the effects caused by the EEF on the QT we observed an inversion of the Arrhenius equation, deactivation of the molecular fluxionality, and stabilization or instantaneous decomposition of the system. All these effects may well be achieved, literally, at the flick of a switch.

Graphical abstract: Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields

Back to tab navigation

Supplementary files

Article information


Submitted
16 Nov 2020
Accepted
15 Dec 2020
First published
15 Dec 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2021,12, 3179-3187
Article type
Edge Article

Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields

O. Kirshenboim, A. Frenklah and S. Kozuch, Chem. Sci., 2021, 12, 3179
DOI: 10.1039/D0SC06295B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements