The term is used to identify two radicals in close proximity in solution, within a solvent cage. They may be formed simultaneously by some unimolecular process, e.g. peroxide decomposition, or they may have come together by diffusion. While the radicals are together, correlation of the unpaired electron spins of the two species cannot be ignored: this correlation is responsible for the CIDNP phenomenon. A radical pair is called geminate provided that each radical partner is a descendant of the same parental pair.
See also: geminate recombination
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PAC, 1995, 67, 1307. 'Glossary of class names of organic compounds and reactivity intermediates based on structure (IUPAC Recommendations 1995)' on page 1363 (https://doi.org/10.1351/pac199567081307)
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