Issue 4, 2022

Frontier orbital stability of nitroxyl organic radicals probed by means of inner shell resonantly enhanced valence band photoelectron spectroscopy

Abstract

We have investigated the frontier orbitals of persistent organic radicals known as nitroxyls by resonant photoelectron spectroscopy (ResPES) under inner shell excitation. By means of this site-specific technique, we were able to disentangle the different atomic contributions to the outer valence molecular orbitals and examine several core–hole relaxation pathways involving the singly occupied molecular orbital (SOMO) localized on the nitroxyl group. To interpret the ResPES intensity trends, especially the strong enhancement of the SOMO ionized state at the N K-edge, we computed the Dyson spin orbitals (DSOs) pertaining to the transitions between the core-excited initial states and several of the singly ionized valence final states. We found that the computed vertical valence ionization potentials and norms of the DSOs are reasonably reliable when based on the long-range corrected CAM-B3LYP density functional. Thanks to their unpaired electrons, nitroxyls have recently found application in technological fields implying a spin control, such as spintronics and quantum computing. The present findings on the electronic structure of nitroxyl persistent radicals furnish important hints for their implementation in technological devices and, more in general, for the synthesis of new and stable organic radicals with tailored properties.

Graphical abstract: Frontier orbital stability of nitroxyl organic radicals probed by means of inner shell resonantly enhanced valence band photoelectron spectroscopy

Supplementary files

Article information

Article type
Paper
Submitted
17 Nov 2021
Accepted
22 Dec 2021
First published
22 Dec 2021

Phys. Chem. Chem. Phys., 2022,24, 1993-2003

Frontier orbital stability of nitroxyl organic radicals probed by means of inner shell resonantly enhanced valence band photoelectron spectroscopy

R. Totani, I. Ljubić, A. Ciavardini, C. Grazioli, F. Galdenzi, M. de Simone and M. Coreno, Phys. Chem. Chem. Phys., 2022, 24, 1993 DOI: 10.1039/D1CP05264K

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