The thermodynamic stability of various alkoxy/aryloxy/peroxy radicals, as well as TEMPO and triplet dioxygen has been explored at a variety of theoretical levels. The effects of hydrogen bonding interactions on the stability of oxygen-centered radicals have been probed by addition of a single solvating water molecule.

Abstract

The 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 RSE_theor and RSE_exp 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.