Issue 7, 2024

Benchmarking the anisotropy of nitroxyl radical solvation with IR spectroscopy

Abstract

Two simple nitroxyl radicals, di-tert-butyl nitroxyl (DTBN) and 2,2,6,6-tetramethylpiperidinyloxyl (TEMPO) are solvated by one or two water, methanol, tert-butyl alcohol or phenol molecules. The resulting low temperature IR spectra of the vacuum-isolated microsolvates in the OH stretching range are assigned based on harmonic DFT predictions for closed shell solvent dimers and trimers and their offset from experiment, to minimise theory-guided assignment bias. Systematic conformational preferences for the first and second solvent molecule are observed, depending on the conformational rigidity of the radical. These assignments are collected into an experimental benchmark data set and used to assess the spectral predicting power of different DFT approaches. The goal is to find inexpensive computational methods which provide reliable spectral predictions for this poorly explored class of microsolvates.

Graphical abstract: Benchmarking the anisotropy of nitroxyl radical solvation with IR spectroscopy

Supplementary files

Article information

Article type
Paper
Submitted
21 Nov 2023
Accepted
24 Jan 2024
First published
26 Jan 2024
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2024,26, 5822-5829

Benchmarking the anisotropy of nitroxyl radical solvation with IR spectroscopy

E. M. Brás, C. Zimmermann, R. Fausto and M. A. Suhm, Phys. Chem. Chem. Phys., 2024, 26, 5822 DOI: 10.1039/D3CP05668F

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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