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The Effect of Medium On Cidnp Kinetics in Geminate Recombination of Biradicals. Experiment and Calculation

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image of Research on Chemical Intermediates

Submicrosecond flash-CIDNP was used to study the dependences of the kinetics and amplitude of CIDNP, arising in biradicals produced in the photolysis of cyclic aliphatic ketones on the temperature and viscosity of the medium. It has been found that for biradicals the geminate CIDNP increases with the diffusion coefficient of the medium. The theoretical considemtion of geminate recombination kinetics is based on the numerical solution of the stochastic Liouville equation for the Fourier transform of the spin density matrix. The dependences of nuclear polarization on the lifetime of the triplet state of initial ketone, on electronic paramagnetic relaxation times, on scavenging rate, and on exchange interaction have been analyzed and compared with erperimental data The conditions of quantum beats manifestation in CIDNP kinetics have been considered theoretically.

Affiliations: 1: Institute of Chemical Kinetics and Combustion and International Tomographic Centre Novosibirsk, 630090, Institutskaya str. 3, Russia


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