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

Autori
Totani, Roberta ; Ljubić, Ivan ; Ciavardini, Alessandra ; Grazioli, Cesare ; Galdenzi, Federico ; de Simone, Monica ; Coreno, Marcello

Izvornik
PCCP. Physical chemistry chemical physics (1463-9076) 24 (2022); 1993-2003

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Nitroxyl radicals ; Core Electron Spectroscopy ; Resonantly Enhanced Photoelectron Spectroscopy ; Density Functional Theory ; Time-dependent Density Functional Theory ; Dyson Orbitals

Sažetak
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

Izvorni jezik
Engleski

Znanstvena područja
Fizika, Kemija

POVEZANOST RADA