On the Nature of Interactions of Radicals with Polar Molecules

Solvated radicals play an important role in many areas of chemistry, but to date, the nature of their interactions with polar solvent molecules lacks chemical interpretation. We present a computational quantum chemical analysis of the binding motives of binary complexes involving electron-poor and electron-rich radicals bound to water and hydrogen fluoride, considered here as model polar solvent molecules. By comparing the binding strengths of several open-shell and closed-shell complexes, in combination with natural localized molecular orbital analysis, we show that open-shell complexes can exhibit additional donor-acceptor interactions relative to analogous closed-shell systems. This may explain the unexpectedly large binding energies observed in some open-shell complexes. These exploratory results show that specific interactions in open-shell systems deserve more attention, and they imply that the quantum mechanical description of explicit solvent molecules needs to be considered carefully when designing simulation protocols for solvated radicals.