Hyperfine coupling dependence of the effects of weak magnetic fields on the recombination reactions of radicals generated from polymerisation photoinitiators.
The recombination reactions of free radicals formed from the photolysis of a series of polymerisation photoinitiators were studied using time-resolved infrared spectroscopy. All molecules showed Zeeman magnetic field effects (MFEs) in the field range 0-37 mT and those molecules that produced radical pairs with average hyperfine couplings greater than 5 mT showed substantial inverted field effects at fields of less than 10 mT (so-called low field effects, LFEs). Monte Carlo simulations with full treatment of all the isotropic hyperfine couplings in the spin Hamiltonian reproduced well the observed field effects. The use of the usual analysis based on the calculated B1/2 value for the radical pair was found to be inappropriate in systems with substantial LFEs, but simple correlations between this B1/2 value and the observed field features were established.
Department of Chemistry, University of Leicester, University Road, Leicester, UK. jrw16@le.ac.uk
Jonathan R
JR
Woodward
Claire B
CB
Vink
D001555:Benzene Derivatives / Q000737:chemistry*; D003511:Cyclohexanols / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D006860:Hydrogen Bonding; D007659:Ketones / Q000737:chemistry*; D008280:Magnetics; D015394:Molecular Structure; D009010:Monte Carlo Method; D010777:Photochemistry; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared / Q000295:instrumentation / Q000379:methods; D013997:Time Factors
D001555:Benzene Derivatives; D003511:Cyclohexanols; D005609:Free Radicals; D007659:Ketones