Issue 9, 2021

Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields

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

Supplementary files

Article information

Article type
Edge Article
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
Creative Commons BY license

Chem. Sci., 2021,12, 3179-3187

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. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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