Journal of Physical Chemistry A, Vol.105, No.34, 8011-8017, 2001
Microwave-induced quantum beats in micellized radical pairs under spin-locking conditions
The effect of short microwave pulse irradiation on the spin correlated radical pairs generated by the hydrogen abstraction reaction of triplet excited xanthone with tert-butyl-substituted phenols in a micellar sodium dodecyl sulfate solution is investigated by a time-resolved transient optical absorption technique. An increase in the microwave pulse duration under the electron spin resonant conditions leads to the alternation of the radical pair concentration. It is explained by the periodical change of the radical pair spin state population with an angular frequency of omega (1) = gamma B-e(1) due to the pumping with resonant microwave field B-1. The double frequency (2 omega (1)) quantum beats are observed under spin-locking conditions. The behavior of quantum beats in this case is rationalized by the effect of microwave pulse on the electron spins of both radicals in the radical pair and reflects the spin dynamics in the triplet manifold of radical pairs that is isolated from that of the singlet during the microwave pulse by the spin-locking effect. Theoretical analysis of the double frequency beats is performed and shows that the spin dephasing process between the triplet states of the radical pair (triplet-triplet dephasing) is the main cause of the double beats decay. Modulation of electron-electron interradical and electron-nuclear intraradical (anisotropy of hyperfine coupling) dipole-dipole interactions by molecular dynamics is considered as a possible source of the triplet-triplet dephasing.