Abstract
Free radicals produced by flash-photolysis can be identified from their electron spin resonance spectra at times exceeding a microsecond after the flash. If they are produced by reaction from triplet precursors and observed within their spin-lattice relaxation time the spectra may be completely in emission. This results from a true spin-polarization process in contrast to the spin-sorting characteristic of radical-pair processes at high magnetic fields. The time-evolution of the signal at a single magnetic field value yields measurements of the degree of polarization and of the rates of the relaxation and kinetic processes associated with the radical; the electron spin-lattice relaxation time in the triplet precursor can be deduced.
The spin-polarization can be transmitted from the primary radical by sufficiently fast reaction to secondary and successive radicals thus disclosing radical reaction pathways to other radicals. This provides complementary mechanistic information to CIDNP which shows pathways to diamagnetic products. Secondary polarization can be used to produce radicals with non-equilibrium spin populations in great variety for relaxation and kinetic studies.
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© 1977 D. Reidel Publishing Company, Dordrecht, Holland
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McLauchlan, K.A. (1977). Flash-Photolysis Electron Spin Resonance. In: Muus, L.T., Atkins, P.W., McLauchlan, K.A., Pedersen, J.B. (eds) Chemically Induced Magnetic Polarization. Nato Advanced Study Institutes Series, vol 34. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-1265-2_8
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DOI: https://doi.org/10.1007/978-94-010-1265-2_8
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