F-cluster: Reaction-induced spin correlation in multi-radical systems

We provide a theoretical analysis of spin-selective recombination processes in clusters of n ≥ 3 radicals. Specifically, we discuss how spin correlation can ensue from random encounters of n radicals, i.e., "F-clusters" as a generalization of radical F-pairs, acting as precursors of spin-driven magnetic field effects. Survival probabilities and the spin correlation of the surviving radical population, as well as transients, are evaluated by expanding the spin density operator in an operator basis that is closed under application of the Haberkorn recombination operator and singlet-triplet dephasing. For the primary spin cluster, the steady-state density operator is found to be independent of the details of the recombination network, provided that it is irreducible; pairs of surviving radicals are triplet-polarized independent of whether they are actually reacting with each other. The steady state is independent of the singlet-triplet dephasing, but the kinetics and the population of sister clusters of smaller size can depend on the degree of dephasing. We also analyze reaction-induced singlet-triplet interconversion in radical pairs due to radical scavenging by initially uncorrelated radicals ("chemical Zeno effect"). We generalize previous treatments for radical triads by discussing the effect of spin-selective recombination in the original pair and extending the analysis to four radicals, i.e., radical pairs interacting with two radical scavengers.