Issue 16, 2023

Hydrogen sharing between two nitroxyl radicals in the gas phase and other microsolvation effects on the infrared spectrum of a bulky hydroxylamine

Abstract

The sterically hindered nitroxyl radical TEMPO is co-expanded with its hydroxylamine TEMPO-H in a supersonic jet and probed by FTIR spectroscopy. One major and one minor conformation of the 1 : 1 complex are identified by their OH stretching signatures, the major one exhibiting a weaker hydrogen bond. The acidic hydrogen atom in these structures can switch between the two TEMPO units in a more or less symmetric double minimum potential with a high barrier. Both conformations are experimentally shown to have a self-exchange quantum tunnelling period longer than 15 ps or 1500 OH vibrational periods even when excited by 41 kJ mol−1 along the OH stretching coordinate. The homodimer and more tentatively the monohydrate of TEMPO-H are also identified in the spectrum.

Graphical abstract: Hydrogen sharing between two nitroxyl radicals in the gas phase and other microsolvation effects on the infrared spectrum of a bulky hydroxylamine

Supplementary files

Article information

Article type
Paper
Submitted
14 3 2023
Accepted
04 4 2023
First published
05 4 2023
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2023,25, 11324-11330

Hydrogen sharing between two nitroxyl radicals in the gas phase and other microsolvation effects on the infrared spectrum of a bulky hydroxylamine

T. L. Fischer, M. A. Tepaske and M. A. Suhm, Phys. Chem. Chem. Phys., 2023, 25, 11324 DOI: 10.1039/D3CP01156A

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