Basic principles and applications of

(a brief review)

Maria Vyushkova

Notre Dame Radiation Laboratory, April 2011 Outline

 What is spin chemistry? Definition, history & introductory notes

pairs, radical pair reaction mechanism, spin correlation in a pair

 Methods of radical pair generation/detection of products

 CIDEP and CIDNP

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Methods of radical pair generation

To create radicals, it usually requires the input of external energy:

 UV/visible light (photochemical generation)

photo-CIDNP – the most ubiquitous spin chemistry technique SNP, RYDMR, MARY, time resolved EPR

 Ionizing irradiation ()

radiofluorescence techniques: OD EPR, MARY, quantum beats ; time resolved EPR

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 Absorbing of photosensitizer in a “transparent” solvent => selective and uniform production of the excited solute molecules

 Decomposition/ transfer of the excited state (S1 or T1) of the precursor

 Both singlet and triplet-born radical pairs (ISC mechanism)

Generation of radical pairs by ionizing radiation:

 an “overkill” method in terms of photon/particle energy

 each photon/particle produces many ionizations/excited states along its track

 the “bulk” solvent molecules are ionized/excited

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References (what to read on spin chemistry)

1. K.M. Salikhov, Yu.N. Molin, R.Z. Sagdeev, A.L. Buchachenko. Spin Polarization and Magnetic Effects in Radical Reactions. Elsevier, Amsterdam-Oxford-New York-Tokyo, 1984

2. U.E. Steiner and T. Ulrich. Magnetic Field Effects in and Related Phenomena // Chem. Rev. 1989, 89, p, 51-147

3. H. Hayashi. Introduction to Dynamic Spin Chemistry. Magnetic Field Effects on Chemical and Biochemical Reactions. World Scientific, 2004

4. J.R. Woodward. Radical Pairs in Solution. //Progress in Reaction Kinetics and Mechanism, 2002, 27, p. 65-207

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