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• W2031854466 startingPage "1386" @default.
• W2031854466 abstract "A method is reported for measuring the recombination efficiency of secondary geminate radical cage pairs. The procedure involves measuring the recombination efficiency for primary geminate recombination (F(c1)) using pump-probe laser methods and measuring the apparent (or net) recombination efficiency (F(cP)) for all geminate pairs (primary and secondary) using steady-state irradiation methods. A mathematical relationship between F(cP), F(c1), and F(c2) (where F(c2) is the recombination efficiency for secondary geminate recombination) is derived and demonstrated using the photolysis reactions of the [(CpR)Mo(CO)(3)](2) molecules, where CpR = eta(5)-C(5)H(4)CH(3) and eta(5)-C(5)H(4)(CH(2))(2)C(O)NCH(3)(CH(2))(n)CH(3) (n = 3, 8, 13, 18). As an example of the results obtained using the new method, it was found that F(c1) = 0.43 and F(c2) = 0.68 for the molecule with CpR = eta(5)-C(5)H(4)CH(2)CH(2)N(CH(3))C(O)(CH(2))(18)CH(3). The value of F(c2) decreased as the side-chain on the Cp ring got shorter; F(c2) is equal to 0.0 for the molecules with n = 3 and for CpR = eta(5)-C(5)H(4)CH(3). It is hypothesized that a longer side-chain prevents facile diffusion of the radicals out of the secondary cage, whereas the smaller side-chains permit more facile diffusion apart of the radicals. A general conclusion is that the reactions of large radicals in particular may be especially impacted by secondary geminate cage recombination." @default.
• W2031854466 created "2016-06-24" @default.
• W2031854466 creator A5014979734 @default.
• W2031854466 creator A5051548173 @default.
• W2031854466 date "2008-11-01" @default.
• W2031854466 modified "2023-10-18" @default.
• W2031854466 title "Radical cage effects: A method for measuring recombination efficiencies of secondary geminate radical cage pairs using pump-probe transient absorption methods" @default.
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• W2031854466 doi "https://doi.org/10.1039/b804399j" @default.
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