The stability of oxygen‐centered radicals and its response to hydrogen bonding interactions

Abstract

AbstractThe stability of various alkoxy/aryloxy/peroxy radicals, as well as TEMPO and triplet dioxygen (3O2) has been explored at a variety of theoretical levels. Good correlations between RSEtheor and RSEexp are found for hybrid DFT methods, for compound schemes such as G3B3‐D3, and also for DLPNO‐CCSD(T) calculations. The effects of hydrogen bonding interactions on the stability of oxygen‐centered radicals have been probed by addition of a single solvating water molecule. While this water molecule always acts as a H‐bond donor to the oxygen‐centered radical itself, it can act as a H‐bond donor or acceptor to the respective closed‐shell parent.